KR20200133209A - Processed product manufacturing method and adhesive laminate - Google Patents

Abstract

It has a base material (Y1) and a pressure-sensitive adhesive layer (X1), and a thermally expandable pressure-sensitive adhesive sheet (I) containing thermally expandable particles in any layer, and a pressure-sensitive adhesive sheet (II) having a base material (Y2) and pressure-sensitive adhesive layer (X2) And, as a method of manufacturing a processed product using an adhesive laminate formed by directly laminating the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), wherein the surface of the adhesive layer (X1) of the adhesive laminate is a support A step of attaching an object to be processed on the surface of the pressure-sensitive adhesive layer (X2) of the adhesive layered body while sticking to (1) a step of performing one or more processing on the object to be processed (2) the thermal expansion start temperature of the thermally expandable particles While maintaining the state in which the object to be processed is affixed to the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive laminate by heating in the above, the pressure-sensitive adhesive laminate is attached to the adhesive sheet (I) and the substrate of the adhesive sheet (II) ( Step of separating at the interface of Y2) in order (3), and further performing at least any of cutting and grinding on the surface opposite to the affixed surface of the object to be processed with the adhesive layer (X2) (4) The manufacturing method of a processed product performed in process (2) or after process (3).

Description

Processed product manufacturing method and adhesive laminate

The present invention relates to a method for manufacturing a processed product in which at least any of cutting and grinding has been performed, and to an adhesive laminate used in the manufacturing method.

The pressure-sensitive adhesive sheet may be used not only for semi-permanently fixing members, but also for temporary fixing applications for temporarily fixing target members when processing or inspecting building materials, interior materials, and electronic parts, and the like.

The adhesive sheet for such a temporary fixing application is required to have both adhesiveness during use and peelability after use.

For example, Patent Document 1 discloses a heat-release type pressure-sensitive adhesive sheet for temporary fixation at the time of cutting an electronic component, in which a thermally expandable adhesive layer containing thermally expandable microspheres is formed on at least one side of a substrate.

In this heat-removable adhesive sheet, the maximum particle diameter of the thermally expandable microspheres is adjusted with respect to the thickness of the thermally expandable adhesive layer, and the average roughness of the center line of the surface of the thermally expandable adhesive layer before heating is adjusted to 0.4 µm or less.

In Patent Literature 1, the heat-release type pressure-sensitive adhesive sheet can secure a contact area with an adherend when cutting an electronic component, and thus can exhibit adhesiveness that can prevent adhesion problems such as chip scattering, On the other hand, there is a description to the effect of being able to easily peel off after use by heating to expand the thermally expandable microspheres and reducing the contact area with the adherend.

Japanese Patent No. 3594853

In the process of processing using the pressure-sensitive adhesive sheet described in Patent Document 1, the object to be processed using the pressure-sensitive adhesive sheet (hereinafter, also referred to as ``processing object'') is temporarily fixed, and after a predetermined processing is performed on the object to be processed, the The object to be processed is separated from the adhesive sheet.

By the way, especially in manufacture of an electronic component, etc., a plurality of processing steps including at least any of a step of cutting an object to be processed and a step of grinding are often performed.

Therefore, for example, for the object to be processed temporarily fixed to the pressure-sensitive adhesive sheet, after at least any of the process of cutting and grinding the object to be processed is performed, the object to be processed is separated from the adhesive sheet and separated The processed object may be affixed to a new adhesive sheet and provided to the next step.

In addition, for the object to be processed temporarily fixed to the adhesive sheet, after processing processes other than the process of cutting and grinding the object to be processed are performed, the object to be processed is separated from the adhesive sheet, and the separated object to be processed is a new adhesive sheet. It is affixed to, and at least any of the process of cutting the object to be processed and the process of grinding may be performed.

However, if a product is manufactured in the same order as described above, not only the work becomes complicated, but also leads to a decrease in productivity of the product. Therefore, it is desired to establish a method capable of improving the productivity of the product while suppressing the work complexity.

In the present invention, the object to be processed is fixed to a support body, and after processing the object to be processed, the object to be processed can be easily separated from the support body with a slight force, and the processing separated from the support body The object can be provided for processing in the next step while the object is affixed to the adhesive sheet, and at least any of the cutting and grinding of the object to be processed can be performed at at least any timing before and after separation of the object to be processed from the support. , A method of manufacturing a processed product in which at least any of cutting and grinding has been performed, and an adhesive laminate for manufacturing a processed product having at least any of cutting and grinding.

The present inventors have a substrate and a pressure-sensitive adhesive layer, a thermally expandable pressure-sensitive adhesive sheet (I) comprising a layer containing thermally expandable particles in a certain layer, and a pressure-sensitive adhesive sheet (II) having a substrate and a pressure-sensitive adhesive layer, It has been found that the above problem can be solved by producing a processed product subjected to at least any processing of cutting and grinding using an adhesive laminate formed by directly laminating the substrate of the sheet (I) and the adhesive sheet (II).

That is, the present invention relates to the following [1] to [17].

[1] A thermally expandable adhesive sheet (I) having a substrate (Y1) and an adhesive layer (X1) and containing thermally expandable particles having a thermal expansion initiation temperature (t) in any layer, and a substrate (Y2) and an adhesive layer (X2) ) Having a pressure-sensitive adhesive sheet (II), and at least any of cutting and grinding is performed using an adhesive laminate formed by directly laminating the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II). As a method of manufacturing a processed product,

Having the following steps (1) to (3) in this order,

Process (1): a step of affixing the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and affixing the object to be processed on the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate

Process (2): A process of performing one or more processing on the object to be processed

Step (3): The adhesiveness while maintaining a state in which the object to be processed is affixed to the surface of the adhesive layer (X2) of the adhesive laminate by heating at or above the thermal expansion initiation temperature (t) of the thermally expandable particles. Step of separating the laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II)

In addition, it has the following process (4),

Process (4): A process of performing at least one of cutting and grinding on the surface of the object to be processed on the opposite side of the surface to be adhered to the adhesive layer (X2)

The said process (4) is performed in at least any one of following (X) and (Y), The manufacturing method of a processed product.

(X): As the one or more processing, it is carried out in the step (2).

(Y): It is implemented after the said process (3)

[2] The production method according to [1], wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270°C.

[3] The manufacturing method according to [1] or [2], wherein the substrate (Y1) of the adhesive sheet (I) has a thermally expandable base material layer (Y1-1) containing the thermally expandable particles.

[4] The production method according to [3], wherein the base material (Y1) of the adhesive sheet (I) has a thermally expandable base material layer (Y1-1) and a non-thermal expandable base material layer (Y1-2).

[5] The above [3] or [4], wherein the thermally expandable substrate layer (Y1-1) of the substrate (Y1) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. The manufacturing method described in.

[6] The adhesive sheet (I) has a configuration in which the substrate (Y1) is sandwiched by the first adhesive layer (X11) and the second adhesive layer (X12), and the first adhesive layer (X11) of the adhesive sheet (I) ) And the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated, and the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is a surface that is affixed to the support. The production method according to [5].

[7] The first adhesive layer (X11) is a thermally expandable adhesive layer containing the thermally expandable particles,

The second pressure-sensitive adhesive layer (X12) is a non-heat-expandable pressure-sensitive adhesive layer, and the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. The production method according to [1] or [2], wherein the surface of the second pressure-sensitive adhesive layer (X12) of (I) is a surface affixed to the support.

[8] The manufacturing method according to [6] or [7], wherein the surface on the side of the substrate (Y1) on which the first pressure-sensitive adhesive layer (X11) is laminated is a surface subjected to an easily adhesive treatment.

[9] The manufacturing method according to the above [1] to [8], wherein the surface on the side on which the adhesive sheet (I) of the substrate (Y2) is laminated is a surface subjected to a peeling treatment.

[10] The production method according to [1] to [9], wherein the adhesive sheet (II) has an intermediate layer (Z2) between the substrate (Y2) and the adhesive layer (X2).

[11] The production method according to [1] to [10], wherein the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is an energy ray-curable pressure-sensitive adhesive layer.

[12] The production method according to [1] to [11], wherein the pressure-sensitive adhesive sheet (II) satisfies one or more of the following requirements (α) to (γ).

-Requirement (α): The Young's modulus of the substrate (Y2) is 1.0 MPa or more.

-Requirement (β): The thickness of the substrate (Y2) is 5 µm or more.

Requirement (γ): The storage modulus G'(23°C) of the pressure-sensitive adhesive layer (X2) is 0.1 MPa or more.

[13] the object to be processed is a semiconductor wafer,

The one or more processing in the step (2) includes the following step (2-A),

Process (2-A): A process of forming a modified region serving as a division starting point on the semiconductor wafer

The said process (4) is the following process (4-A),

Process (4-A): The process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2)

The manufacturing method according to the above [1] to [12], wherein the step (4-A) is performed in at least any one of the following (X-A) or (Y-A).

(X-A): The one or more processing is performed after the step (2-A)

(Y-A): It is carried out after the above step (3)

[14] the object to be processed is a semiconductor chip,

The one or more processing in the step (2) includes the following step (2-B),

Process (2-B): of the adhesive surfaces of the semiconductor chip and the pressure-sensitive adhesive layer (X2), the peripheral portion of the semiconductor chip is covered with a sealing material, the sealing material is cured, and the semiconductor chip Step of obtaining a cured encapsulant formed by encapsulating the cured encapsulant

The manufacturing method according to the above [1] to [12], wherein the step (4) is performed in at least any one of the following (X-B) and (Y-B).

(X-B): The one or more processing is performed after the step (2-B)

(Y-B): It is carried out after the above step (3)

[15] a semiconductor wafer having a modified region in which the object to be processed is a division starting point,

The production method according to [1] to [12], wherein the step (4) is the following step (4-A).

Process (4-A): The process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2)

[16] the object to be processed is a semiconductor wafer having a cut groove that becomes a division starting point,

The production method according to [1] to [12], wherein the step (1) is the following step (1-C), and the step (4) is the following step (4-C).

Step (1-C): A surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate is affixed to the support, and the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive laminate has a cutout groove of the semiconductor wafer Process of attaching

Process (4-C): A process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2)

[17] A pressure-sensitive adhesive sheet (II) having a substrate (Y1) and a pressure-sensitive adhesive layer (X1), a thermally expandable pressure-sensitive adhesive sheet (I) containing thermally expandable particles in a certain layer, and a substrate (Y2) and pressure-sensitive adhesive layer (X2) ), wherein the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) are directly laminated to each other to produce a processed article subjected to at least any processing of cutting and grinding.

According to the present invention, after the object to be processed is fixed to the support body and the object to be processed is processed, the object to be processed can be easily separated from the support body with a slight force, and the object separated from the support body The object to be processed can be provided for processing in the next step while the object to be processed is affixed to the adhesive sheet, and at least any of the cutting and grinding of the object to be processed can be performed at at least any timing before and after separation of the object to be processed from the support. It is possible to provide a method for manufacturing a processed product in which at least any of cutting and grinding has been performed, and an adhesive laminate for manufacturing a processed product in which at least any of cutting and grinding has been performed.

1 is a schematic cross-sectional view of the adhesive laminate, showing the configuration of the adhesive laminate according to the first embodiment used in the production method of the present invention.
Fig. 2 is a schematic cross-sectional view of the adhesive laminate, showing the configuration of the adhesive laminate according to the second aspect used in the production method of the present invention.
3 is a schematic cross-sectional view of the adhesive laminate, showing the configuration of the adhesive laminate according to the third embodiment used in the production method of the present invention.
4 is a schematic diagram showing an example of the manufacturing method of the present invention.
5 is a schematic diagram showing another example of the manufacturing method of the present invention.

In this specification, whether the "layer" is a "non-thermal expandable layer" or a "heat expandable layer" is determined as follows.

The target layer is heat-treated for 3 minutes at the expansion start temperature (t) of the thermally expandable particles contained in the layer containing the thermally expandable particles. When the volume change rate calculated from the following equation is less than 5%, the layer is judged as a "non-thermal expandable layer", and when it is 5% or more, the layer is judged as a "thermally expandable layer".

Volume change rate (%) = {(volume of the layer after heat treatment-volume of the layer before heat treatment)/volume of the layer before heat treatment} × 100

In addition, a layer not containing thermally expandable particles is referred to as a "non-thermal expandable layer".

In this specification, the "active ingredient" refers to a component excluding a diluting solvent among components contained in a target composition.

In this specification, the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically, is a value measured based on the method described in Examples.

In this specification, for example, "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid", and other similar terms are also the same.

In the present specification, with respect to a preferred numerical range (for example, a range of content, etc.), the lower limit and upper limit values described step by step can be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", a combination of "preferable lower limit value (10)" and "more preferable upper limit value (60)" to "10 to 60" You may.

[Method of manufacturing processed products]

The manufacturing method of the processed article of this invention has a base material (Y1) and an adhesive layer (X1), and the thermally expandable adhesive sheet (I) containing thermally expandable particles of the thermal expansion initiation temperature (t) in any layer, and the base material ( Cutting and grinding using an adhesive laminate comprising an adhesive sheet (II) having Y2) and an adhesive layer (X2), and directly laminating the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) As a method of manufacturing a processed product subjected to at least any of the processing,

Having the following steps (1) to (3) in this order,

Process (1): a step of affixing the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and affixing the object to be processed on the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate

Process (2): A process of performing one or more processing on the object to be processed

Step (3): The adhesiveness while maintaining a state in which the object to be processed is affixed to the surface of the adhesive layer (X2) of the adhesive laminate by heating at or above the thermal expansion initiation temperature (t) of the thermally expandable particles. Step of separating the laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II)

In addition, it has the following process (4),

Process (4): A process of performing at least one of cutting and grinding on the surface of the object to be processed on the opposite side of the surface to be adhered to the adhesive layer (X2)

The said process (4) is implemented in at least any one of following (X) and (Y).

(X): As the one or more processing, it is carried out in the step (2).

(Y): It is implemented after the said process (3)

Hereinafter, after describing the adhesive laminate used in the manufacturing method of the present invention, each manufacturing process including the steps (1) to (4) will be described.

[Configuration of adhesive laminate]

The adhesive laminate used in the manufacturing method of the present invention has a substrate (Y1) and an adhesive layer (X1), and contains thermally expandable particles in a layer, a thermally expandable adhesive sheet (I), and a substrate (Y2), When the pressure-sensitive adhesive sheet (II) having the pressure-sensitive adhesive layer (X2) is provided, the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated, and a predetermined processing is performed on the object to be processed. It is used to fix the object to be processed on the support.

In this specification, the predetermined processing means processing in the step (2) in the manufacturing method of the present invention. In addition, in the present invention, the step (4) may be performed as one of one or more processing in the step (2). Therefore, the predetermined processing can also include step (4) in the manufacturing method of the present invention.

In the adhesive laminate used in the manufacturing method of the present invention, the surface of the adhesive layer (X1) of the adhesive sheet (I) is a surface to which the support is attached. When the pressure-sensitive adhesive sheet (I) has a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12), the surface of the second pressure-sensitive adhesive layer (X12) is a surface to which the support is attached, and that of the first pressure-sensitive adhesive layer (X11) The surface is a surface laminated on the substrate (Y2) side of the pressure-sensitive adhesive sheet (II). Moreover, the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is a surface to which the object to be processed is affixed.

And the adhesive laminate used in the manufacturing method of the present invention is heat-treated at a temperature equal to or higher than the expansion initiation temperature (t) of the thermally expandable particles, so that the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) ) At the interface P. In the following description, the heat treatment is also referred to as "separation heat treatment".

1 to 3 are schematic cross-sectional views each showing the configuration of the adhesive laminate of the first aspect, the second aspect, and the third aspect used in the production method of the present invention.

<The adhesive laminate of the first aspect>

As the adhesive laminate of the first aspect to be used in the manufacturing method of the present invention, for example, the adhesive laminates 1a and 1b shown in Figs. 1(a) and (b) can be mentioned.

The adhesive laminate (1a, 1b) is provided with an adhesive sheet (I) having a substrate (Y1) and an adhesive layer (X1), and an adhesive sheet (II) having a substrate (Y2) and an adhesive layer (X2), The base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) have a structure in which the base material (Y2) is directly laminated.

In the adhesive laminate used in the manufacturing method of the present invention, any layer of the pressure-sensitive adhesive sheet (I) is made into a layer containing thermally expandable particles so that it can be separated at the interface P by the heat treatment for separation.

In the adhesive laminate used in the manufacturing method of the present invention, thermally expandable particles are expanded by the heat treatment for separation, and irregularities are formed on the surface of the layer containing the thermally expandable particles. Thereby, the contact area between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) decreases.

As a result, after affixing the object to be processed on the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) and performing predetermined processing, the interface P of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) By separating at, the object to be processed in a state affixed to the pressure-sensitive adhesive sheet (II) can be obtained.

Therefore, according to the manufacturing method of the present invention, a predetermined processing can be performed by fixing the object to be processed to a support through the above-described adhesive laminate, and the object to be processed is subjected to a predetermined processing with a slight force. It can be easily separated collectively from the support. In addition, the object to be processed separated from the support can be provided to the next step as it is while being affixed to the pressure-sensitive adhesive sheet (II).

Accordingly, there is no need to perform the operation of affixing the object to be processed after separation on which the predetermined processing has been performed to a new adhesive sheet, and thus workability and productivity of the product can be improved.

In the first aspect of the present invention, it is preferable that the substrate (Y1) has a thermally expandable base layer (Y1-1) containing thermally expandable particles, like the adhesive laminate (1a, 1b) shown in FIG. .

In addition, the base material (Y1) may have a single-layer configuration having only a thermally expandable base material layer (Y1-1) containing thermally expandable particles, like the adhesive laminate (1a) shown in Fig. 1(a). In addition, the base material (Y1) may be a multilayer structure having a thermally expandable base material layer (Y1-1) and a non-thermal expandable base material layer (Y1-2) as in the adhesive laminate (1b) shown in FIG. 1(b). .

In the adhesive layered product 1a shown in FIG. 1(a), the heat-expandable particles contained in the thermally expandable base layer (Y1-1) constituting the base material (Y1) expand by heat treatment for separation, and the base material ( The surface of the adhesive sheet (II) of Y1) is uneven, and the contact area between the substrate (Y1) and the substrate (Y2) of the adhesive sheet (II) decreases.

On the other hand, since the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive layered product (1a) is affixed to the support, irregularities are hardly formed on the surface of the pressure-sensitive adhesive layer (X1) side of the substrate (Y1). Thereby, the unevenness|corrugation can be formed efficiently on the surface of the base material (Y1) in contact with the adhesive sheet (II).

As a result, the adhesive layered product 1a can be easily separated collectively at the interface P of the substrate Y1 of the pressure-sensitive adhesive sheet (I) and the substrate Y2 of the pressure-sensitive adhesive sheet (II) with a slight force.

In addition, by forming the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive layered product 1a from a pressure-sensitive adhesive composition having a high adhesive force to the support, it may be designed so that it can be more easily separated from the interface P.

In addition, in the adhesive layered product 1b shown in FIG. 1(b), thermally expandable particles included in the thermally expandable base layer (Y1-1) constituting the base material (Y1) are expanded by heat treatment for separation, Unevenness occurs on the surface of the substrate Y1 on the side of the pressure-sensitive adhesive sheet II, and the contact area between the substrate Y1 and the substrate Y2 of the pressure-sensitive adhesive sheet II decreases.

On the other hand, since the non-thermal expandable substrate layer (Y1-2) constituting the substrate (Y1) has a small degree of expansion by heat treatment, irregularities are not well formed on the surface of the adhesive layer (X1) side of the substrate (Y1). Does not. Thereby, the unevenness|corrugation can be formed efficiently on the surface of the adhesive sheet (II) side of the base material (Y1).

As a result, the adhesive layered product 1b can be easily separated collectively with a slight force at the interface P between the substrate Y1 of the adhesive sheet (I) and the substrate Y2 of the adhesive sheet (II).

In addition, in the same manner as in the case of the adhesive laminate (1a), by forming the pressure-sensitive adhesive layer (X1) of the adhesive laminate (1b) with a pressure-sensitive adhesive composition that increases the adhesion to the support, it is possible to more easily separate from the interface P. It can also be designed to fit.

From the above point of view, in the first aspect of the present invention, like the adhesive laminate (1b) shown in Fig. 1(b), the substrate (Y1) has a thermally expandable substrate layer (Y1-1) on one surface side. It is preferable that it has, and has a non-thermal expandable base material layer (Y1-2) on the other surface side.

In addition, in the first aspect of the present invention, from the viewpoint of making the adhesive laminate that can be easily separated collectively with a slight force from the interface P, the adhesive laminate (1a, 1b) has It is preferable that it is a structure in which the heat-expandable base material layer (Y1-1) of the base material (Y1) and base material (Y2) of the adhesive sheet (II) are laminated directly.

<Second aspect adhesive laminate>

As the adhesive laminate of the second aspect to be used in the production method of the present invention, for example, the adhesive laminate (1c, 1d) shown in Figs. 2(a) and (b) can be mentioned.

The adhesive laminate (1c, 1d) has a configuration in which the adhesive sheet (I) is sandwiched between the substrate (Y1) by the first adhesive layer (X11) and the second adhesive layer (X12), and the adhesive sheet (I) The first pressure-sensitive adhesive layer (X11) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.

In addition, in the adhesive laminate (1c, 1d), the surface of the second adhesive layer (X12) becomes a surface to be affixed to the support.

In the second aspect of the present invention, it is preferable that the substrate (Y1) has a thermally expandable base layer (Y1-1) containing thermally expandable particles, like the adhesive laminate (1c, 1d) shown in FIG. .

In addition, the base material (Y1) may have a single-layer configuration having only the thermally expandable base material layer (Y1-1) containing thermally expandable particles, as in the adhesive laminate (1c) shown in Fig. 2(a).

In addition, the base material (Y1) may be a multilayer structure having a thermally expandable base material layer (Y1-1) and a non-thermal expandable base material layer (Y1-2) as in the adhesive laminate (1d) shown in FIG. 2(b). .

Moreover, when the base material (Y1) is a multilayered structure having a thermally expandable base material layer (Y1-1) and a non-thermal expandable base material layer (Y1-2), the thermally expandable base material layer (Y1-1) is an adhesive sheet (II) It is arranged on the side, and it is preferable that the non-thermal expandable base material layer (Y1-2) is arranged on the side of the second pressure-sensitive adhesive layer (X12).

In the adhesive laminate (1c) shown in Fig. 2(a), the thermally expandable particles in the thermally expandable base layer (Y1-1) constituting the base material (Y1) expand by heat treatment for separation, and the base material (Y1) The unevenness is formed on the surface of the 1st adhesive layer (X11) side of. And the 1st adhesive layer X11 is also pushed up by the unevenness|corrugation generated on the surface of the base material Y1, and the unevenness|corrugation is also formed in the surface of the adhesive sheet II side of the 1st adhesive layer X11. Thereby, the contact area between the 1st adhesive layer (X11) and the base material (Y2) of the adhesive sheet (II) decreases.

On the other hand, since the support is affixed to the second pressure-sensitive adhesive layer X12, irregularities are hardly formed on the surface of the second pressure-sensitive adhesive layer X12 side of the substrate Y1. Therefore, irregularities are efficiently formed on the surface of the first adhesive layer (X11) side of the substrate (Y1), and irregularities are efficiently formed on the surface of the first adhesive layer (X11) on the adhesive sheet (II) side.

As a result, the adhesive laminate (1c) is easily separated collectively with a slight force at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II). It becomes possible.

Further, by forming the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive layered product 1c from a pressure-sensitive adhesive composition that increases the adhesive strength to the support, it may be designed so that it can be more easily separated from the interface P.

In addition, in the adhesive laminate (1d) shown in FIG. 2(b), thermally expandable particles included in the thermally expandable base layer (Y1-1) constituting the base material (Y1) expand by heat treatment for separation, Unevenness is generated on the surface of the substrate (Y1) on the side of the first pressure-sensitive adhesive layer (X11). And the 1st adhesive layer X11 is also pushed up by the unevenness|corrugation generated on the surface of the base material Y1, and the unevenness|corrugation is also formed in the surface of the adhesive sheet II side of the 1st adhesive layer X11. Thereby, the contact area between the 1st adhesive layer (X11) and the base material (Y2) of the adhesive sheet (II) decreases.

On the other hand, since the non-thermal expandable base layer (Y1-2) constituting the base material (Y1) has a small degree of expansion due to heat treatment, the surface of the base material (Y1) on the side of the second pressure-sensitive adhesive layer (X12) has good irregularities. Is not formed. Thereby, the unevenness|corrugation can be formed efficiently on the surface of the 1st adhesive layer (X11) side of the base material (Y1).

As a result, the adhesive laminated body 1d can be easily separated collectively with a slight force at the interface P between the base material Y1 of the adhesive sheet (I) and the base material Y2 of the adhesive sheet (II).

In addition, in the same manner as in the case of the adhesive laminate (1c), by forming the second adhesive layer (X12) of the adhesive laminate (1d) from a pressure-sensitive adhesive composition that increases the adhesive strength to the support, at the interface P, more easily It can also be designed to be detachable.

Here, also in the second aspect of the present invention, from the viewpoint of making the adhesive laminate that can be easily separated collectively with a slight force than at the interface P, the adhesive laminate (1c, 1d) has the adhesive sheet (I). It is preferable that it is a structure in which the thermally expandable base material layer (Y1-1) of the base material (Y1) and the 1st adhesive layer (X11) were laminated directly. In this case, it is more preferable that the first adhesive layer (X11) and the substrate (Y2) of the resin film-forming sheet (II) are directly laminated.

<3rd aspect adhesive laminate>

The adhesive laminates (1a, 1b) of the first aspect and the adhesive laminates (1c, 1d) of the second aspect used in the production method of the present invention are all one of the layers constituting the substrate (Y1), and are thermally expanded. It includes a layer containing sexual particles.

On the other hand, as the adhesive laminate of the third aspect to be used in the production method of the present invention, a thermally expandable adhesive layer containing the thermally expandable particles is formed on the surface of the interface P side of the substrate (Y1) of the adhesive sheet (I). It may be a configuration in which a non-thermal expandable pressure-sensitive adhesive layer is formed on the other surface of the substrate (Y1).

In such an aspect, for example, like the adhesive laminated body 2 shown in FIG. 3, the adhesive sheet (I) is the base material (Y1) by the 1st adhesive layer (X11) and the 2nd adhesive layer (X12). The first adhesive layer (X11) is a thermally expandable adhesive layer containing thermally expandable particles, and the second adhesive layer (X12) is a non-thermal expandable adhesive layer, and the adhesive sheet (I) What has a structure in which the 1 adhesive layer (X11) and the base material (Y2) of the adhesive sheet (II) laminated directly is mentioned.

In addition, in the above-described configuration as in the adhesive layered product 2, the surface of the second adhesive layer X12 is a surface to be affixed to the support.

Moreover, in the above-described configuration as in the adhesive laminate (2), the substrate (Y1) is preferably a non-thermal expandable substrate.

In the adhesive laminate (2) shown in FIG. 3, by the heat treatment for separation, irregularities are formed on the surface of the thermally expandable adhesive layer, which is the first adhesive layer (X11), and the first adhesive layer (X11) and the adhesive sheet ( The contact area of the substrate (Y2) of II) decreases.

On the other hand, on the surface of the first pressure-sensitive adhesive layer (X11) on the side of the substrate (Y1), since the substrate (Y1), which is a non-thermal expandable substrate, is laminated, irregularities are hardly generated. Therefore, the unevenness|corrugation is formed efficiently on the surface of the adhesive sheet (II) side of 1st adhesive layer (X11).

As a result, the adhesive laminate (2) is easily separated collectively with a slight force at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II). It becomes possible.

<Configuration of adhesive laminate with peeling material>

In one aspect of the adhesive laminate used in the production method of the present invention, on one or both of the surface of the pressure-sensitive adhesive layer (X1) to which the support is affixed and the surface of the pressure-sensitive adhesive layer (X2) to which the object to be processed is adhered In addition, it may be a configuration in which a release material is laminated.

In addition, for example, in the adhesive laminate (1a, 1b) shown in Figs. 1(a) and (b), peeling treatment is performed on both surfaces on one of the adhesive surfaces of the adhesive layer (X1) and the adhesive layer (X2). What is laminated|stacked by the implemented release material may be made into the structure wound up in a roll shape. The adhesive laminate (1c, 1d) shown in Figs. 2(a) and (b) and the adhesive laminate (2) shown in Fig. 3 may be similarly wound in a roll shape.

[Various properties of adhesive laminate]

The adhesive laminate of one aspect used in the manufacturing method of the present invention is heat-treated at a temperature equal to or higher than the expansion initiation temperature (t) of the thermally expandable particles, so that the adhesive sheet (I) and the base material of the adhesive sheet (II) ( At the interface P of Y2), it becomes possible to easily separate all at once with a slight force.

Here, in the adhesive laminate of one aspect of the present invention, by heat treatment at a temperature equal to or higher than the expansion initiation temperature (t) of the thermally expandable particles, the peel force (F ₁ ) when separating at the interface P is usually 0 to 2000 mN/25 mm, preferably 0 to 1000 mN/25 mm, more preferably 0 to 150 mN/25 mm, still more preferably 0 to 100 mN/25 mm, even more preferably 0 to It is 50 mN/25 mm.

In addition, when the peeling force (F ₁ ) is 0 mN/25 mm, even if the peeling force is to be measured by the method described in Examples, the peeling force is too small, and thus the measurement is impossible.

In addition, from the viewpoint of sufficiently fixing the object to be processed before heat treatment so as not to adversely affect the processing operation, it is preferable that the interlayer adhesiveness between the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) is high.

From the above point of view, in the adhesive laminate of one aspect to be used in the production method of the present invention, the peeling force (F ₀ ) at the time of separation at the interface P before heat treatment is preferably 100 It is mN/25 mm or more, more preferably 300 mN/25 mm or more, still more preferably 500 mN/25 mm or more, and preferably 50000 mN/25 mm or less.

In one aspect of the adhesive laminate used in the manufacturing method of the present invention, the peel force (F ₀ ) is greater than the peel force (F ₁ ). Specifically, the ratio of the peeling force (F ₁ ) and the peeling force (F ₀ ) [(F ₁ )/(F ₀ )] is preferably 0 to 0.9, more preferably 0 to 0.8, further preferably Is 0 to 0.5, and even more preferably 0 to 0.2.

In addition, as a temperature condition when measuring the peeling force (F ₁ ), it is not less than the expansion initiation temperature (t), and may be a temperature at which the thermally expandable particles expand.

Moreover, as a temperature condition when measuring the peeling force (F ₀ ), it just needs to be less than the expansion start temperature (t), but it is basically room temperature (23 degreeC).

However, more specific measurement conditions and measurement methods of peeling force (F ₁ ) and peeling force (F ₀ ) are based on the methods described in Examples.

In the pressure-sensitive adhesive laminate of one aspect used in the production method of the present invention, the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) at room temperature (23°C) (the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive The adhesive force of the layer (X12)) and the adhesive force of the adhesive layer (X2) of the adhesive sheet (II) are each independently, preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/ It is 25 mm, more preferably 0.4 to 6.0 N/25 mm, and even more preferably 0.5 to 4.0 N/25 mm.

When the adhesive sheet (I) has a first adhesive layer (X11) and a second adhesive layer (X12), the adhesive strength of the first adhesive layer (X11) and the second adhesive layer (X12) is preferably in the above range, respectively. However, from the viewpoint of improving the adhesion with the support and making it possible to separate more easily collectively at the interface P, the adhesive strength of the second adhesive layer (X12) affixed to the support is the adhesive force of the first adhesive layer (X11) It is more preferable to be higher.

The substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) are non-adhesive substrates.

In the present invention, the determination of whether or not a non-adhesive substrate is performed when the probe tack value measured in accordance with JIS Z0237: 1991 is less than 50 mN/5 mmφ with respect to the surface of the target substrate. It is judged to be an adhesive substrate”.

The probe tack value on the surface of the substrate (Y1) of the adhesive sheet (I) used in the embodiment of the present invention and the substrate (Y2) of the adhesive sheet (II) are each independently, usually 50 mN/5 mm It is less than φ, but is preferably less than 30 mN/5 mmφ, more preferably less than 10 mN/5 mmφ, and still more preferably less than 5 mN/5 mmφ.

In addition, in this specification, the specific measuring method of the probe tack value on the surface of a thermally expandable base material is according to the method described in Examples.

Hereinafter, each layer constituting the adhesive laminate of the present invention will be described.

[Configuration of adhesive sheet (I)]

The adhesive sheet (I) of the adhesive laminate used in the manufacturing method of the present invention has a substrate (Y1) and an adhesive layer (X1), and is separated from the adhesive sheet (II) with the substrate (Y2) by heating treatment for separation. It is a thermally expandable pressure-sensitive adhesive sheet containing thermally expandable particles in a certain layer so that it can be separated at the interface.

In one aspect of the present invention, the thermal expansion start temperature (t) of the thermally expandable particles is preferably 60 to 270°C.

As the pressure-sensitive adhesive sheet (I) used in one aspect of the present invention, the ones of the following aspects are preferable.

PSA sheet (I) of first aspect: PSA sheet (I) having a thermally expandable base material layer (Y1-1) containing thermally expandable particles as a base material (Y1).

PSA sheet (I) of the second aspect: On both sides of the substrate (Y1), a first PSA layer (X11) as a thermally expandable PSA layer containing thermally expandable particles, and a second PSA layer that is a non-heat expandable PSA layer ( The adhesive sheet (I) having X12).

-The adhesive sheet (I) in which the base material (Y1) is a non-thermal expandable base material.

Hereinafter, the adhesive sheet (I) of the first aspect and the second aspect used in one aspect of the present invention will be described.

<Adhesive sheet (I) of the first aspect>

As the pressure-sensitive adhesive sheet (I) of the first aspect, as shown in Figs. 1-2, the substrate (Y1) has a thermally expandable base material layer (Y1-1) containing thermally expandable particles.

In the pressure-sensitive adhesive sheet (I) of the first aspect, from the viewpoint of enabling easy separation at the interface P between the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) with a slight force, the pressure-sensitive adhesive layer (X1) It is preferable that it is a non-thermal expandable adhesive layer.

Specifically, in the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminates 1a and 1b shown in FIG. 1, it is preferable that the pressure-sensitive adhesive layer (X1) is a non-heat expandable pressure-sensitive adhesive layer. Moreover, in the adhesive sheet (I) which the adhesive laminated body (1c, 1d) shown in FIG. 2 has, it is preferable that both the 1st adhesive layer (X11) and the 2nd adhesive layer (X12) are a non-thermal expandable adhesive layer. .

The thickness of the substrate (Y1) before the heat treatment for separation of the pressure-sensitive adhesive sheet (I) of the first aspect is preferably 10 to 1000 µm, more preferably 20 to 700 µm, still more preferably 25 to 500 µm, more More preferably, it is 30 to 300 micrometers.

The thickness of the pressure-sensitive adhesive layer (X1) before heat treatment for separation of the pressure-sensitive adhesive sheet (I) of the first aspect is preferably 1 to 60 µm, more preferably 2 to 50 µm, still more preferably 3 to 40 µm, Even more preferably, it is 5 to 30 micrometers.

In addition, in this specification, for example, as shown in FIG. 2, when the adhesive sheet (I) has a plurality of adhesive layers, the "thickness of the adhesive layer (X1)" is the respective adhesive layers It means the thickness (in FIG. 2, each thickness of the adhesive layer (X11) and (X12)).

In addition, in this specification, the thickness of each layer constituting an adhesive laminate means a value measured by the method described in Examples.

In the pressure-sensitive adhesive sheet (I) of the first aspect, as the thickness ratio [(Y1-1)/(X1)] of the thermally expandable base layer (Y1-1) and the pressure-sensitive adhesive layer (X1) before the heat treatment for separation, It is preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, and even more preferably 30 or less.

If the said thickness ratio is 1000 or less, it can be heat-processed at the interface P between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) at the interface P, and it can be set as an adhesive laminate that can be easily separated in one batch with a slight force. .

In addition, the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and even more preferably 5.0 or more.

In addition, in the pressure-sensitive adhesive sheet (I) of the first aspect, the substrate (Y1) may be composed of only the thermally expandable substrate layer (Y1-1) as shown in FIG. 1(a), and in FIG. 1(b) As shown, it may have a thermally expandable base material layer (Y1-1) on the side of the pressure-sensitive adhesive sheet (II) and a non-thermal expandable base material layer (Y1-2) on the side of the pressure-sensitive adhesive layer (X1).

In the pressure-sensitive adhesive sheet (I) of the first aspect, the thickness ratio of the thermally expandable base layer (Y1-1) and the non-thermal expandable base layer (Y1-2) before heat treatment for separation [(Y1-1)/(Y1 As -2)], Preferably it is 0.02 to 200, More preferably, it is 0.03 to 150, More preferably, it is 0.05 to 100.

<Adhesive sheet (I) of the second aspect>

As the pressure-sensitive adhesive sheet (I) of the second aspect, as shown in FIG. 3, on both sides of the substrate (Y1), respectively, a first pressure-sensitive adhesive layer (X11) which is a heat-expandable pressure-sensitive adhesive layer containing thermally expandable particles, and a specific heat What has the 2nd adhesive layer (X12) which is an expandable adhesive layer is mentioned.

In addition, in the pressure-sensitive adhesive sheet (I) of the second aspect, the first pressure-sensitive adhesive layer (X11), which is a heat-expandable pressure-sensitive adhesive layer, and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are in direct contact with each other.

In addition, in the pressure-sensitive adhesive sheet (I) of the second aspect, it is preferable that the base material (Y1) is a non-thermal expandable base material layer.

In the pressure-sensitive adhesive sheet (I) of the second aspect, the thickness ratio of the first pressure-sensitive adhesive layer (X11) as a heat-expandable pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer (X12) as a non-thermal expandable pressure-sensitive adhesive layer before heat treatment for separation [( As X11)/(X12)], preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.

In addition, in the pressure-sensitive adhesive sheet (I) of the second aspect, the thickness ratio of the first pressure-sensitive adhesive layer (X11) as a thermally expandable pressure-sensitive adhesive layer and the base material (Y1) before heat treatment for separation [(X11)/(Y1) ] As, Preferably it is 0.05-20, More preferably, it is 0.1-10, More preferably, it is 0.2-3.

Hereinafter, after explaining the thermally expandable particles included in any layer constituting the pressure-sensitive adhesive sheet (I), the thermally expandable base layer (Y1-1) constituting the base material (Y1), the non-thermal expandable base material layer (Y1-2), And the pressure-sensitive adhesive layer (X1) will be described in detail.

<Thermal expandable particles>

The thermally expandable particles used in the present invention may be particles that expand by heating, but are preferably particles whose expansion start temperature (t) is adjusted to 60 to 270°C. The expansion start temperature (t) is appropriately selected depending on the use of the adhesive laminate.

For example, in the manufacturing method of the present invention, when the adhesive laminate is not exposed to a high-temperature environment in steps (1) and (2) (for example, a modified region as a division starting point is formed inside the semiconductor wafer) In the case of performing such processing, etc.), it is preferable that the expansion start temperature of the thermally expandable particles is as low as possible within the above temperature range. Thereby, heating energy required when separating the adhesive sheet I and the adhesive sheet 1I can be made small, and the manufacturing cost of a cut product and/or a grinding object can be reduced. Moreover, the adhesive sheet (I) and the adhesive sheet (1I) can be separated without giving an excessive thermal history to the object to be processed.

In this specification, the expansion start temperature (t) of the thermally expandable particles means a value measured based on the following method.

(Measurement method of expansion start temperature (t) of thermally expandable particles)

To an aluminum cup with a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, 0.5 mg of thermally expandable particles to be measured were added, and a sample with an aluminum cover (diameter 5.6 mm, thickness 0.1 mm) raised from the top was prepared. .

Using a dynamic viscoelasticity measuring device, the height of the sample is measured while a force of 0.01 N is applied from the top of the aluminum cover to the sample by a pressurizer. Then, in a state where a force of 0.01 N is applied by a pressurizer, heating is performed from 20°C to 300°C at a heating rate of 10°C/min, and the amount of displacement in the vertical direction of the pressurizer is measured, and the displacement start temperature in the positive direction Is taken as the expansion start temperature (t).

The thermally expandable particles are preferably microencapsulated foaming agents composed of an outer shell made of a thermoplastic resin and an inner shell component that is enclosed in the outer shell and vaporized when heated to a predetermined temperature.

As a thermoplastic resin constituting the outer shell of the microencapsulated foaming agent, for example, vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinyl chloride Liden, polysulfone, etc. are mentioned.

Inclusion components contained in the outer shell include, for example, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclo Propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane , Octadecane, nanodecane, isotridecane, 4-methyldodecane, isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane , Isooctadecane, isonanodecane, 2,6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, penta Decylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc. are mentioned.

These encapsulation components may be used alone or in combination of two or more.

The expansion start temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of the inclusion component.

The average particle diameter before expansion at 23° C. of the thermally expandable particles used in one aspect of the present invention is preferably 3 to 100 μm, more preferably 4 to 70 μm, still more preferably 6 to 60 μm, Even more preferably, it is 10-50 micrometers.

In addition, the average particle diameter before expansion of the thermally expandable particles is the volume median particle diameter (D ₅₀ ), which is measured using a laser diffraction particle size distribution measuring device (e.g., Malvern, product name ``Mastersizer 3000''). , In the particle distribution of the thermally expandable particles before expansion, the cumulative volume frequency calculated from the smaller particle size of the thermally expandable particles before expansion is a particle diameter corresponding to 50%.

The 90% particle diameter (D ₉₀ ) before expansion at 23° C. of the thermally expandable particles used in one aspect of the present invention is preferably 10 to 150 μm, more preferably 20 to 100 μm, and still more preferably Is 25 to 90 µm, even more preferably 30 to 80 µm.

In addition, the 90% particle diameter before expansion of the thermally expandable particles (D ₉₀ ) means thermal expansion before expansion measured using a laser diffraction type particle size distribution measuring device (for example, Malvern's product name ``Mastersizer 3000''). In the particle distribution of the star particles, the cumulative volume frequency calculated from the smaller the particle diameter of the thermally expandable particles before expansion corresponds to 90%.

The maximum volume expansion rate when heated to a temperature equal to or higher than the expansion initiation temperature (t) of the thermally expandable particles used in one aspect of the present invention is preferably 1.5 to 100 times, more preferably 2 to 80 times, and even more preferably Is 2.5 to 60 times, and even more preferably 3 to 40 times.

<Thermal expandable substrate layer (Y1-1)>

In the adhesive laminate of one aspect of the present invention, when the substrate (Y1) of the adhesive sheet (I) has a thermally expandable base layer (Y1-1) containing thermally expandable particles, the thermally expandable base layer (Y1- It is preferable that 1) satisfy|fills the following requirement (1).

Requirement (1): The storage elastic modulus E'(t) of the thermally expandable base layer (Y1-1) at the expansion start temperature (t) of the thermally expandable particles is 1.0×10 ⁷ Pa or less.

In addition, in this specification, the storage modulus E'of the thermally expandable base material layer (Y1-1) at a predetermined temperature means a value measured by the method described in Examples.

The requirement (1) can be said to be an index indicating the rigidity of the thermally expandable base layer (Y1-1) just before the thermally expandable particles expand.

Before expansion of the thermally expandable particles, the storage modulus E'of the thermally expandable base layer (Y1-1) decreases with increasing temperature. However, before and after the expansion initiation temperature (t) of the thermally expandable particles is reached, the thermally expandable particles start to expand, thereby suppressing a decrease in the storage modulus E'of the thermally expandable base layer (Y1-1).

On the other hand, in order to enable easy separation with a slight force at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), by heating to a temperature equal to or higher than the expansion initiation temperature (t), the adhesive sheet ( It is necessary to make it easy to form unevenness|corrugation on the surface of the side which is laminated|stacked with the base material (Y2) of I).

In short, the thermally expandable base material layer (Y1-1) that satisfies the above requirement (1), the thermally expandable particles expand sufficiently at the expansion initiation temperature (t) to become sufficiently large, and laminated with the base material (Y2) of the adhesive sheet (II), Unevenness is likely to be formed on the surface of the pressure-sensitive adhesive sheet (I) on the side.

As a result, at the interface P between the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II), it can be a pressure-sensitive adhesive laminate that can be easily separated collectively with a slight force.

The storage modulus E'(t) specified in the requirement (1) of the thermally expandable base layer (Y1-1) used in the present invention is from the above viewpoint, preferably 9.0 × 10 ⁶ Pa or less, more preferably 8.0 It is × 10 ⁶ Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, and even more preferably 4.0 × 10 ⁶ Pa or less.

In addition, the flow of the expanded thermally expandable particles is suppressed, the shape retention of the irregularities formed on the surface of the pressure-sensitive adhesive sheet (I) on the side to be laminated with the substrate (Y2) of the pressure-sensitive adhesive sheet (II) is improved, and at the interface P From the viewpoint of enabling easier separation with a slight force, the storage elastic modulus E'(t) specified in the requirement (1) of the thermally expandable base layer (Y1-1) is preferably 1.0×10 ³ Pa or more, It is more preferably 1.0 × 10 ⁴ Pa or more, and still more preferably 1.0 × 10 ⁵ Pa or more.

From the viewpoint of making the thermally expandable base layer (Y1-1) satisfying the above requirement (1), the content of the thermally expandable particles in the thermally expandable base layer (Y1-1) is the whole of the thermally expandable base layer (Y1-1). The mass (100 mass%) is preferably 1 to 40 mass%, more preferably 5 to 35 mass%, still more preferably 10 to 30 mass%, and even more preferably 15 to 25 mass%.

In addition, from the viewpoint of improving the interlayer adhesion between the thermally expandable base layer (Y1-1) and the other layer to be laminated, the surface of the thermally expandable base layer (Y1-1) is subjected to surface treatment by an oxidation method or an uneven method, and easy adhesion. Treatment or primer treatment may be performed.

Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment, and as the unevenness method, for example, a sand blast method, The solvent treatment method etc. are mentioned.

It is preferable to form the thermally expandable base material layer (Y1-1) from a resin composition (y) containing a resin and thermally expandable particles.

In addition, the resin composition (y) may contain, if necessary, an additive for a substrate within a range that does not impair the effects of the present invention.

Examples of the additive for the substrate include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an anti-blocking agent, and a colorant.

In addition, these additives for substrates may be used alone or in combination of two or more.

In the case of containing these additives for substrates, the content of each additive for substrates is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass based on 100 parts by mass of the resin.

About the thermally expandable particles contained in the resin composition (y) which is a material for forming the thermally expandable base layer (Y1-1), it is as described above.

The content of the thermally expandable particles is preferably 1 to 40 mass%, more preferably 5 to 35 mass%, still more preferably 10 with respect to the total amount (100 mass%) of the active ingredient of the resin composition (y). It is-30 mass %, More preferably, it is 15-25 mass %.

The resin contained in the resin composition (y) which is a material for forming the thermally expandable base layer (Y1-1) may be a non-adhesive resin or an adhesive resin.

In short, the resin contained in the resin composition (y) may be an adhesive resin, and in the process of forming the thermally expandable base layer (Y1-1) from the resin composition (y), the adhesive resin undergoes a polymerization reaction with a polymerizable compound. , The obtained resin becomes a non-adhesive resin, and the thermally expandable base layer (Y1-1) containing the resin may have non-adhesive properties.

The mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1000 to 1 million, more preferably 1000 to 700,000, and still more preferably 1000 to 500,000.

Further, when the resin is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.

The content of the resin is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, further preferably 65 to 90 with respect to the total amount (100% by mass) of the active ingredient of the resin composition (y). It is mass %, More preferably, it is 70 to 85 mass %.

In addition, from the viewpoint of forming the thermally expandable base layer (Y1-1) that satisfies the above requirement (1), the resin included in the resin composition (y) is one selected from acrylic urethane resins and olefin resins. It is preferable to include the above.

Moreover, as said acrylic urethane-type resin, the following resin (U1) is preferable.

An acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth)acrylic acid ester.

(Acrylic urethane resin (U1))

Examples of the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.

In addition, it is preferable that the urethane prepolymer (UP) is obtained by further carrying out a chain extension reaction using a chain extender.

Examples of the polyol used as the raw material of the urethane prepolymer (UP) include an alkylene type polyol, an ether type polyol, an ester type polyol, an esteramide type polyol, an ester/ether type polyol, and a carbonate type polyol.

These polyols may be used alone or in combination of two or more.

As the polyol used in one aspect of the present invention, a diol is preferable, an ester type diol, an alkylene type diol and a carbonate type diol are more preferable, and an ester type diol and a carbonate type diol are still more preferable.

Examples of the ester-type diol include alkanedols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; Alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; One or two or more selected from diols such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4,4'-dicar Acid, succinic acid, adipic acid, azelaic acid, sebacic acid, hetic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid , Dicarboxylic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and methylhexahydrophthalic acid, and one or more condensation polymers selected from anhydrides thereof.

Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, Polybutylenehexamethylene adipate diol, polydiethylene adipate diol, poly(polytetramethylene ether) adipate diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, poly Butylene azelate diol, polybutylene sebacate diol, polyneopentyl terephthalate diol, and the like.

Examples of the alkylene diol include alkanedols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; Alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; Polyalkylene glycol, such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; Polyoxyalkylene glycols such as polytetramethylene glycol; And the like.

As a carbonate type diol, for example, 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, 1,3-propylene Carbonate diol, 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, and the like.

Examples of the polyvalent isocyanate used as the raw material for the urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

These polyhydric isocyanates may be used alone or in combination of two or more.

Further, these polyvalent isocyanates may be trimethylolpropane adduct-type modified products, biuret-type modified products reacted with water, and isocyanurate-type modified products containing an isocyanurate ring.

Among these, as the polyvalent isocyanate used in one aspect of the present invention, diisocyanate is preferable, and 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI) , 2,6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and at least one selected from alicyclic diisocyanate is more preferable.

As the alicyclic diisocyanate, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane Diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc. are mentioned, but isophorone diisocyanate (IPDI) is preferable.

In one aspect of the present invention, the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) is a reaction product of a diol and a diisocyanate, and a linear urethane prepolymer having ethylenic unsaturated groups at both ends is preferable. Do.

As a method of introducing ethylenically unsaturated groups at both ends of the linear urethane prepolymer, the NCO group at the terminal of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth)acrylate are reacted. A method to let you do is mentioned.

As hydroxyalkyl (meth)acrylate, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2- Hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. are mentioned.

As a vinyl compound which becomes the side chain of the acrylic urethane resin (U1), (meth)acrylic acid ester is contained at least.

As the (meth)acrylic acid ester, at least one selected from alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate is preferable, and alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate are used in combination. It is more preferable to do it.

When using alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in combination, the blending ratio of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 It is -100 parts by mass, more preferably 0.5 to 30 parts by mass, still more preferably 1.0 to 20 parts by mass, even more preferably 1.5 to 10 parts by mass.

The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and even more preferably 1 to 3.

Moreover, as a hydroxyalkyl (meth)acrylate, the thing similar to the hydroxyalkyl (meth)acrylate used to introduce ethylenic unsaturated groups to both ends of the linear urethane prepolymer mentioned above is mentioned.

Examples of vinyl compounds other than (meth)acrylic acid ester include aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; Polar group-containing monomers, such as vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and meth(acrylamide); And the like.

These may be used alone or in combination of two or more.

The content of the (meth)acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and even more preferably based on the total amount (100% by mass) of the vinyl compound. It is 80 to 100 mass%, More preferably, it is 90 to 100 mass%.

The total content of alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably based on the total amount (100% by mass) of the vinyl compound. Is 65 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.

The acrylic urethane resin (U1) used in one aspect of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth)acrylic acid ester, and polymerizing both.

In the polymerization, it is preferable to further add a radical initiator to carry out.

In the acrylic urethane resin (U1) used in one aspect of the present invention, the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11) As /(u12)], in a mass ratio, preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, even more preferably It is 35/65-55/45.

(Olefin resin)

As the resin contained in the resin composition (y), as an olefin-based resin, which is preferable, it is a polymer having at least a structural unit derived from an olefin monomer.

As the olefin monomer, an α-olefin having 2 to 8 carbon atoms is preferable, and specifically, ethylene, propylene, butylene, isobutylene, 1-hexene and the like are exemplified.

Among these, ethylene and propylene are preferable.

As a specific olefin resin, for example, ultra-low density polyethylene (VLDPE, density: 880 kg/m 3 or more and less than 910 kg/m 3 ), low density polyethylene (LDPE, density: 910 kg/m 3 or more and less than 915 kg/m 3), Polyethylene resins such as medium-density polyethylene (MDPE, density: 915 kg/m3 or more and less than 942 kg/m3), high-density polyethylene (HDPE, density: 942 kg/m3 or more), and linear low-density polyethylene; Polypropylene resin (PP); Polybutene resin (PB); Ethylene-propylene copolymer; Olefin elastomer (TPO); Poly(4-methyl-1-pentene) (PMP); Ethylene-vinyl acetate copolymer (EVA); Ethylene-vinyl alcohol copolymer (EVOH); Olefinic terpolymers such as ethylene-propylene-(5-ethylidene-2-norbornene); And the like.

In one aspect of the present invention, the olefin-based resin may be a modified olefin-based resin further subjected to one or more modifications selected from acid modification, hydroxyl group modification, and acrylic modification.

For example, examples of the acid-modified olefin-based resin obtained by performing acid modification on an olefin-based resin include a modified polymer obtained by graft polymerization of an unsaturated carboxylic acid or an anhydride thereof to the above-described unmodified olefin-based resin. I can.

Examples of the unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic anhydride, and anhydride. Itaconic acid, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, etc. are mentioned.

Moreover, unsaturated carboxylic acid or its anhydride may be used individually and may use 2 or more types together.

As the acrylic-modified olefin-based resin obtained by performing acrylic modification on the olefin-based resin, a modified polymer obtained by graft polymerization of alkyl (meth)acrylate as a side chain to the above-described unmodified olefin-based resin as a main chain is used. Can be lifted.

The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 12.

As said alkyl (meth)acrylate, the same thing as the compound selectable as a monomer (a1') mentioned later is mentioned, for example.

Examples of the hydroxyl group-modified olefin-based resin obtained by subjecting the olefin-based resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-described unmodified olefin-based resin as the main chain.

Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl Hydroxyalkyl (meth)acrylates such as (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Unsaturated alcohols, such as vinyl alcohol and allyl alcohol, etc. are mentioned.

(Resin other than acrylic urethane resin and olefin resin)

In one aspect of the present invention, the resin composition (y) may contain resins other than the acrylic urethane-based resin and the olefin-based resin within a range that does not impair the effects of the present invention.

Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polystyrene; Acrylonitrile-butadiene-styrene copolymer; Cellulose triacetate; Polycarbonate; Polyurethane which does not correspond to acrylic urethane resin; Polysulfone; Polyether ether ketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resins such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine-based resins and the like.

However, from the viewpoint of forming the thermally expandable base layer (Y1-1) that satisfies the above requirement (1), the content ratio of resins other than the acrylic urethane-based resin and olefin-based resin in the resin composition (y) is preferably small. .

The content ratio of resins other than the acrylic urethane resin and the olefin resin is preferably less than 30 parts by mass, more preferably less than 20 parts by mass, based on 100 parts by mass of the total amount of the resin contained in the resin composition (y). , More preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass.

(Solvent-free resin composition (y1))

As an aspect of the resin composition (y) used in one aspect of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50000 or less, an energy ray polymerizable monomer, and the above-described thermally expandable particles are blended. Solvent-free resin composition (y1) which is formed and does not contain a solvent can be mentioned.

In the solvent-free resin composition (y1), no solvent is blended, but the energy ray polymerizable monomer contributes to the improvement of the plasticity of the oligomer.

It is easy to form the thermally expandable base layer (Y1-1) satisfying the above requirement (1) by irradiating the coating film formed with the solvent-free resin composition (y1) with energy rays.

In addition, the kind and shape of the thermally expandable particles to be blended in the solvent-free resin composition (y1), and the blending amount (content) are as described above.

The mass average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50000 or less, but preferably 1000 to 50000, more preferably 2000 to 40000, still more preferably 3000 to 35000, even more Preferably it is 4000 to 30000.

Further, as the oligomer, it is sufficient to have an ethylenically unsaturated group having a mass average molecular weight of 50000 or less among the resins contained in the resin composition (y) described above, but the urethane prepolymer (UP) described above is preferable.

Further, as the oligomer, a modified olefin-based resin having an ethylenically unsaturated group can also be used.

The total content of the oligomer and the energy ray polymerizable monomer in the solvent-free resin composition (y1) is preferably 50 to 99 mass% with respect to the total amount (100 mass%) of the solvent-free resin composition (y1). , More preferably, they are 60 to 95 mass%, still more preferably 65 to 90 mass%, and even more preferably 70 to 85 mass%.

As an energy ray polymerizable monomer, for example, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate , Cyclohexyl (meth)acrylate, adamantane (meth)acrylate, and alicyclic polymerizable compounds such as tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate, and phenol ethylene oxide-modified acrylate; Heterocyclic polymerizable compounds, such as tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, N-vinylpyrrolidone, and N-vinyl caprolactam, etc. are mentioned.

These energy ray polymerizable monomers may be used alone or in combination of two or more.

The content ratio of the oligomer and the energy ray polymerizable monomer [oligomer/energy ray polymerizable monomer] in the solvent-free resin composition (y1) is a mass ratio, preferably 20/80 to 90/10, more It is preferably 30/70 to 85/15, more preferably 35/65 to 80/20.

In one aspect of the present invention, it is preferable that the solvent-free resin composition (y1) is formed by further mixing a photopolymerization initiator.

By containing the photoinitiator, the curing reaction can be sufficiently advanced even by irradiation of relatively low energy energy rays.

As a photoinitiator, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethyl thiuram mono Sulfide, azobisisobutyronitrile, dibenzyl, diacetyl, 8-chloranthraquinone, and the like.

These photoinitiators may be used independently and may use 2 or more types together.

The blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, still more preferably 0.02 with respect to the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer. It is-3 parts by mass.

<Non-thermal expandable substrate layer (Y1-2)>

As a material for forming the non-thermal expandable substrate layer (Y1-2) constituting the substrate (Y1), for example, a paper material, a resin, a metal, etc. can be mentioned, and the adhesive laminate of one aspect of the present invention It can be appropriately selected according to the use of.

Examples of the paper material include thin paper, heavy paper, fine paper, impregnated paper, coated paper, art paper, sulfuric acid paper, glassine paper, and the like.

Examples of the resin include polyolefin resins such as polyethylene and polypropylene; Vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polystyrene; Acrylonitrile-butadiene-styrene copolymer; Cellulose triacetate; Polycarbonate; Urethane resins such as polyurethane and acrylic-modified polyurethane; Polymethylpentene; Polysulfone; Polyether ether ketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resins such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine-based resins and the like.

Examples of the metal include aluminum, tin, chromium, and titanium.

These forming materials may be constituted by one type or may be used in combination of two or more types.

As the non-thermal expandable substrate layer (Y1-2) in which two or more types of forming materials are used in combination, the paper material is laminated with a thermoplastic resin such as polyethylene, or a resin film containing a resin or a metal film is formed on the surface of the sheet. Can be lifted.

In addition, as a method of forming a metal layer, for example, a method of depositing the metal by a PVD method such as vacuum deposition, sputtering, or ion plating, or a method of affixing a metal foil made of the metal using a general adhesive. Can be mentioned.

In addition, from the viewpoint of improving the interlayer adhesion between the non-thermal expandable base layer (Y1-2) and the other layer to be laminated, when the non-thermal expandable base layer (Y1-2) contains a resin, the non-thermal expandable base layer (Y1-2) Also on the surface of the thermally expandable base layer (Y1-1) described above, a surface treatment by an oxidation method or an uneven method, an easy adhesion treatment, or a primer treatment may be performed.

Moreover, when the non-thermal expandable base material layer (Y1-2) contains a resin, you may contain the above-mentioned additive for base materials which can also be contained in the resin composition (y) together with the said resin.

The non-thermal expandable base layer (Y1-2) is a non-thermal expandable layer judged based on the method described above.

Therefore, the volume change ratio (%) of the non-thermal expandable base layer (Y1-2) calculated from the above-described formula is less than 5%, but is preferably less than 2%, more preferably less than 1%, and more preferably Is less than 0.1%, even more preferably less than 0.01%.

In addition, the non-thermal expandable base material layer (Y1-2) may contain thermally expandable particles as long as the volume change ratio is within the above range. For example, by selecting the resin contained in the non-thermal expandable base layer (Y1-2), even if the thermally expandable particles were contained, it is possible to adjust the volume change rate to the above range.

However, the smaller the content of the thermally expandable particles in the non-thermal expandable base layer (Y1-2), the more preferable.

The specific content of the thermally expandable particles is usually less than 3% by mass, preferably less than 1% by mass, more preferably 0.1% by mass with respect to the total mass (100% by mass) of the non-thermally expandable substrate layer (Y1-2). It is less than, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass. More preferably, thermally expandable particles are not contained in the non-thermally expandable base layer (Y1-2).

<Adhesive layer (X1)>

The pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) used in the first aspect of the present invention can be formed from the pressure-sensitive adhesive composition (x1) containing an adhesive resin.

Moreover, the adhesive composition (x1) may contain additives for adhesives, such as a crosslinking agent, a tackifier, a polymeric compound, and a polymerization initiator, as needed.

Hereinafter, each component contained in the pressure-sensitive adhesive composition (x1) will be described.

In addition, when the adhesive sheet (I) has a first adhesive layer (X11) and a second adhesive layer (X12), the first adhesive layer (X11) and the second adhesive layer (X12) are also shown below. It can be formed from the pressure-sensitive adhesive composition (x1) containing each component.

(Adhesive resin)

As the adhesive resin used in one aspect of the present invention, the resin alone may have adhesiveness and a polymer having a mass average molecular weight (Mw) of 10,000 or more.

As the mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention, from the viewpoint of improving the adhesive strength, preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, even more preferably It is between 30,000 and 1 million.

Examples of specific adhesive resins include rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins.

These adhesive resins may be used alone or in combination of two or more.

Moreover, when these adhesive resins are a copolymer which has 2 or more types of structural units, the form of the said copolymer is not specifically limited, Any of a block copolymer, a random copolymer, and a graft copolymer may be sufficient.

The adhesive resin used in one aspect of the present invention may be an energy ray-curable adhesive resin in which a polymerizable functional group is introduced into the side chain of the adhesive resin.

As said polymerizable functional group, a (meth)acryloyl group, a vinyl group, etc. are mentioned.

Moreover, although ultraviolet rays and electron beams are mentioned as an energy ray, ultraviolet rays are preferable.

In one aspect of the present invention, from the viewpoint of expressing excellent adhesive force, it is preferable that the adhesive resin contains an acrylic resin.

In addition, when using the pressure-sensitive adhesive sheet (I) having the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12), the first pressure-sensitive adhesive layer (X11) in contact with the resin film-forming sheet (II) By containing the resin, it can be made easy to form irregularities on the surface of the first pressure-sensitive adhesive layer.

As the content ratio of the acrylic resin in the adhesive resin, with respect to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x1) or the adhesive layer (X1), preferably 30 to 100% by mass, more preferably Is 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 85 to 100% by mass.

(Acrylic resin)

In one aspect of the present invention, as an acrylic resin that can be used as the adhesive resin, for example, a polymer containing a structural unit derived from an alkyl (meth)acrylate having a linear or branched alkyl group, cyclic And polymers containing structural units derived from (meth)acrylates having a structure.

The mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1.5 million, more preferably 200,000 to 1.3 million, still more preferably 350,000 to 1.2 million, and even more preferably 500,000 to 110. Only.

As the acrylic resin used in one aspect of the present invention, a structural unit (a1) derived from an alkyl (meth)acrylate (a1') (hereinafter also referred to as ``monomer (a1')'') and a functional group-containing monomer (a2) The acrylic copolymer (A1) having the structural unit (a2) derived from') (hereinafter, also referred to as "monomer (a2')") is more preferable.

The number of carbon atoms in the alkyl group of the monomer (a1') is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and even more preferably 4 from the viewpoint of improving adhesion properties. It is ∼ 8.

In addition, the alkyl group which the monomer (a1') has may be a linear alkyl group or a branched chain alkyl group.

As the monomer (a1'), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and Uryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and the like.

These monomers (a1') may be used alone or in combination of two or more.

As the monomer (a1'), butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable.

The content of the structural unit (a1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, and even more preferably based on the total structural unit (100% by mass) of the acrylic copolymer (A1). It is 70 to 97.0 mass%, More preferably, it is 80 to 95.0 mass%.

As a functional group which the monomer (a2') has, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, etc. are mentioned, for example.

In short, examples of the monomer (a2') include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

These monomers (a2') may be used alone or in combination of two or more.

Among these, as the monomer (a2'), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.

As a hydroxyl group-containing monomer, the thing similar to the hydroxyl group-containing compound mentioned above is mentioned, for example.

Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; Ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid, and anhydrides thereof, 2-(acryloyloxy)ethyl succinate, 2-carboxyethyl (meth)acrylate, and the like. .

The content of the constituent unit (a2) is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, still more preferably with respect to the total constituent units (100% by mass) of the acrylic copolymer (A1). It is 1.0 to 30 mass %, More preferably, it is 3.0 to 25 mass %.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').

In addition, in the acrylic copolymer (A1), the content of the structural units (a1) and (a2) is preferably 70 to 100% by mass with respect to the total structural units (100% by mass) of the acrylic copolymer (A1). , More preferably, it is 80 to 100% by mass, still more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.

Examples of the monomer (a3') include olefins such as ethylene, propylene, and isobutylene; Halogenated olefins such as vinyl chloride and vinylidene chloride; Diene-based monomers such as butadiene, isoprene, and chloroprene; Cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl ( (Meth)acrylates having a cyclic structure such as meth)acrylate and imide (meth)acrylate; Styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloylmorpholine, N-vinylpyrrolidone, etc. Can be lifted.

Further, the acrylic copolymer (A1) may be an energy ray-curable acrylic copolymer in which a polymerizable functional group is introduced into the main chain and/or the side chain.

The polymerizable functional group and the energy ray are as described above.

In addition, the polymerizable functional group is a polymerization having an acrylic copolymer having the structural units (a1) and (a2) described above, and a substituent and a polymerizable functional group capable of bonding with the functional group of the structural unit (a2) of the acrylic copolymer. It can be introduced by reacting the sexual compound (Xa).

As the polymerizable compound (Xa), for example, (meth)acryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, (meth)acryloyl isocyanate, allyl isocyanate, glycidyl (Meth)acrylate, (meth)acrylic acid, etc. are mentioned.

(Crosslinking agent)

In one aspect of the present invention, when the pressure-sensitive adhesive composition (x1) contains a pressure-sensitive adhesive resin having a functional group, like the acrylic copolymer (A1) described above, it is preferable to further contain a crosslinking agent.

The crosslinking agent reacts with an adhesive resin having a functional group, and crosslinks the adhesive resins by using the functional group as a crosslinking starting point.

As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned, for example.

These crosslinking agents may be used alone or in combination of two or more.

Among these crosslinking agents, isocyanate-based crosslinking agents are preferred from the viewpoints of increasing cohesive strength and improving adhesive strength, and from the viewpoints of availability and the like.

The content of the crosslinking agent is appropriately adjusted according to the number of functional groups in the adhesive resin, but with respect to 100 parts by mass of the adhesive resin having a functional group, preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, further It is preferably 0.05 to 5 parts by mass.

(Adhesion imparting agent)

In one aspect of the present invention, the pressure-sensitive adhesive composition (x1) may further contain a tackifier from the viewpoint of further improving the adhesive strength.

In the present specification, the term ``tackifier'' refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000 as a component that auxiliaryly improves the adhesive strength of the above-described adhesive resin, and is distinguished from the above-described adhesive resin. will be.

The mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 500 to 8000, and still more preferably 800 to 5000.

As a tackifier, for example, a rosin resin, a terpene resin, a styrene resin, C5 obtained by copolymerizing a C5 fraction such as pentene, isoprene, piperine, and 1,3-pentadiene produced by pyrolysis of petroleum naphtha. Petroleum resins, C9 petroleum resins obtained by copolymerizing C9 fractions such as indene and vinyl toluene produced by thermal decomposition of petroleum naphtha, and hydrogenated resins obtained by hydrogenating these.

The softening point of the tackifier is preferably 60 to 170°C, more preferably 65 to 160°C, and still more preferably 70 to 150°C.

In addition, in this specification, the "softening point" of a tackifier means a value measured in conformity with JIS K 2531.

The tackifier may be used alone, or two or more types having different softening points and structures may be used in combination.

And when using a plurality of tackifiers of two or more types, it is preferable that the weighted average of the softening points of the plurality of tackifiers fall within the above range.

The content of the tackifier is preferably 0.01 to 65% by mass, and more with respect to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x1) or the total mass (100% by mass) of the pressure-sensitive adhesive layer (X1). It is preferably 0.05 to 55% by mass, still more preferably 0.1 to 50% by mass, even more preferably 0.5 to 45% by mass, and even more preferably 1.0 to 40% by mass.

(Photopolymerization initiator)

In one aspect of the present invention, when the pressure-sensitive adhesive composition (x1) contains an energy ray-curable pressure-sensitive adhesive resin as the pressure-sensitive adhesive resin, it is preferable to further contain a photopolymerization initiator.

By setting the pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive resin and a photopolymerization initiator, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition sufficiently advances the curing reaction even by irradiation of relatively low energy energy rays, and adjusts the adhesive force to a desired range. It becomes possible to do.

In addition, as the photoinitiator used in one aspect of the present invention, the same as those blended in the above-described solvent-free resin composition (y1) can be mentioned.

The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.05 to 2 parts by mass per 100 parts by mass of the energy ray-curable adhesive resin.

(Additive for adhesive)

In one aspect of the present invention, the pressure-sensitive adhesive composition (x1) may contain, in addition to the additives described above, an additive for a pressure-sensitive adhesive used for a general pressure-sensitive adhesive within a range that does not impair the effect of the present invention.

Examples of such additives for pressure-sensitive adhesives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), and ultraviolet absorbers.

In addition, these adhesive additives may be used individually, respectively, and may use 2 or more types together.

In the case of containing these additives for pressure-sensitive adhesives, the content of each of the additives for pressure-sensitive adhesives is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin.

In addition, when using the adhesive sheet (I) of the 2nd aspect mentioned above which the adhesive laminated body (2) shown in FIG. 3 has, the 1st adhesive layer (X11) which is a thermally expandable adhesive layer is additionally thermally expandable It is formed from a thermally expandable pressure-sensitive adhesive composition (x11) containing particles.

The thermally expandable particles are as described above.

The content of the thermally expandable particles is preferably 1 to 70% by mass with respect to the total amount (100% by mass) of the active ingredient of the thermally expandable adhesive composition (x11) or the total mass (100% by mass) of the thermally expandable adhesive layer. , More preferably, it is 2 to 60 mass%, More preferably, it is 3 to 50 mass%, Even more preferably, it is 5 to 40 mass%.

On the other hand, when the pressure-sensitive adhesive layer (X1) is a non-heat-expandable pressure-sensitive adhesive layer, the content of the heat-expandable particles in the non-heat-expandable pressure-sensitive adhesive composition as a material for forming the non-heat-expandable pressure-sensitive adhesive layer is preferably as small as possible.

The content of the thermally expandable particles is preferably less than 1% by mass, more preferably with respect to the total amount (100% by mass) of the active ingredient of the non-thermal expandable pressure-sensitive adhesive composition or the total mass (100% by mass) of the non-thermally expandable pressure-sensitive adhesive layer. Is less than 0.1 mass%, more preferably less than 0.01 mass%, and even more preferably less than 0.001 mass%. More preferably, heat-expandable particles are not contained in the non-heat-expandable pressure-sensitive adhesive composition or the non-heat-expandable pressure-sensitive adhesive layer.

In addition, when using the PSA sheet (I) having the first PSA layer (X11) and the second PSA layer (X12), which is a non-thermal expandable PSA layer, as in the PSA laminate (1c, 1d) shown in FIG. 2, The storage shear modulus G'(23) of the first adhesive layer (X11) which is a non-thermal expandable adhesive layer at 23°C is preferably 1.0 × 10 ⁸ Pa or less, more preferably 5.0 × 10 ⁷ Pa or less, More preferably, it is 1.0 × 10 ⁷ Pa or less.

If the storage shear modulus G'(23) of the first adhesive layer (X11) as a non-thermal expandable adhesive layer is 1.0 × 10 ⁸ Pa or less, for example, it has the same configuration as the adhesive laminates (1c, 1d) shown in FIG. In the case of, unevenness is formed on the surface of the first adhesive layer (X11) in contact with the adhesive sheet (II) due to the expansion of the thermally expandable particles in the thermally expandable base layer (Y1-1) by the separation heat treatment. It gets easier. As a result, at the interface P between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II), it is possible to obtain an adhesive laminate that can be easily separated collectively with a slight force.

In addition, the storage shear modulus G'(23) of the first pressure-sensitive adhesive layer (X11) which is a non-thermal expandable pressure-sensitive adhesive layer at 23°C is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5.0 × 10 ⁴ Pa or more. , More preferably 1.0×10 ⁵ Pa or more.

In addition, in this specification, the storage shear modulus G'(23) of an adhesive layer means a value measured by the method described in Examples.

[Configuration of adhesive sheet (II)]

The adhesive sheet (II) of the adhesive laminate used in the production method of the present invention has a base (Y2) and an adhesive layer (X2), and the base (Y2) is directly laminated with the adhesive sheet (I).

In addition, from the viewpoint of improving the interlayer adhesion between the substrate (Y2) and the pressure-sensitive adhesive layer (X2), the surface treatment by the above-described oxidation method or the uneven method, etc., is easily adhered to the surface on the side where the pressure-sensitive adhesive layer of the substrate (Y2) is laminated. Treatment or primer treatment may be performed.

In addition, in the adhesive laminate used in one aspect of the present invention, from the viewpoint of suppressing the adhesion of the residue of the pressure-sensitive adhesive layer (X2) to the cutting object and/or the grinding object, surface irregularities such as a semiconductor wafer having bumps, etc. From the viewpoint of having excellent followability with respect to a large object to be processed, and from the viewpoint of having excellent stability over time of the adhesive force of the adhesive layer (X2), the adhesive sheet (II) is between the substrate (Y2) and the adhesive layer (X2). Eh, it is preferable to have an intermediate layer (Z2).

Moreover, for example, the surface of the adhesive layer X2 side of the base material Y2 may be subjected to antistatic treatment. In the case of having the intermediate layer Z2, the surface of the substrate Y2 on the intermediate layer Z2 side may be subjected to antistatic treatment.

It is preferable that the base material Y2 is a non-thermal expandable base material from the viewpoint of enabling easy separation at the interface P with the pressure-sensitive adhesive sheet (I) at once with a slight force.

In addition, before and after the heat treatment, from the viewpoint of maintaining good adhesion to the adherend, the pressure-sensitive adhesive layer (X2) is also preferably a non-heat expandable pressure-sensitive adhesive layer.

Moreover, it is preferable that the intermediate layer (Z2) is also a non-thermal expandable layer.

Therefore, as the volume change ratio (%) of the base material (Y2), the adhesive layer (X2), and the intermediate layer (Z2) calculated from the above-described formula, each independently, is less than 5%, preferably less than 2%, It is more preferably less than 1%, still more preferably less than 0.1%, and even more preferably less than 0.01%. Moreover, more preferably, thermally expandable particles are not contained in the substrate (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2).

Hereinafter, the base material (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2) will be described.

<Description (Y2)>

As the material for forming the base material (Y2), the same material as the material for forming the non-thermal expandable base layer (Y1-2) described above can be mentioned.

Moreover, it is preferable that the base material (Y2) contains a resin, and it is more preferable that a resin layer containing a resin is formed on the surface of the base material (Y2) on the side to be laminated with the adhesive sheet (I) at least, and the base material It is more preferable that (Y2) is a resin film or a resin sheet.

In addition, from the viewpoint of having a property capable of stably holding the object to be processed, even when grinding the object to be processed ultrathin in the grinding of the object to be processed in step (4), among a resin film or a resin sheet, a polyethylene film, A polypropylene film, an ethylene-vinyl acetate copolymer (EVA) film, and a polyethylene terephthalate film are preferable, and an ethylene-vinyl acetate copolymer (EVA) film is more preferable.

In addition, the resin film or resin sheet described above may contain a known filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and the like.

Moreover, a resin film or a resin sheet may be transparent, and color or metal etc. may be deposited as desired.

Further, from the viewpoint of enabling easy separation at the interface P at once with a slight force after the heat treatment for separation, the surface of the substrate Y2 on the side to be laminated on the pressure-sensitive adhesive sheet I may be subjected to a peeling treatment.

In addition, the base material (Y2) is a viewpoint of making it easy to prevent positional shift when affixing the object to be processed to the pressure-sensitive adhesive layer (X2), and excessive sinking into the pressure-sensitive adhesive layer (X2) when affixing the object to be processed. From the viewpoint of making it easy to prevent, it is preferable that the storage elastic modulus E'(23) at 23°C is 1.0×10 ⁶ Pa or more.

In addition, the base material (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range, but from the above viewpoint, the content of the thermally expandable particles in the base material (Y2) is more preferably smaller.

The content of the thermally expandable particles in the substrate (Y2) is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass with respect to the total mass (100% by mass) of the substrate (Y2). , More preferably less than 0.01% by mass, even more preferably less than 0.001% by mass. More preferably, the thermally expandable particles are not contained in the substrate (Y2).

The thickness of the substrate (Y2) is preferably 5 to 500 µm, more preferably 15 to 300 µm, and still more preferably 20 to 200 µm.

When the thickness of the substrate (Y2) is 5 µm or more, it is easy to make it excellent in deformation resistance (dimensional stability) at high temperature. On the other hand, when the thickness of the substrate is 500 µm or less, deformation of the pressure-sensitive adhesive sheet (II) due to vibration can be suppressed when at least any of cutting and grinding is performed on the object to be processed attached to the pressure-sensitive adhesive sheet (II). Therefore, it is easy to improve processing precision such as film thickness precision.

<Adhesive layer (X2)>

The pressure-sensitive adhesive layer (X2) included in the resin film-forming sheet (II) can be formed using the pressure-sensitive adhesive composition (x1) described above, and a preferable component and a preferable range of the content of each component are also included in the pressure-sensitive adhesive composition (x1). Is the same as

Here, in one aspect of the present invention, the pressure-sensitive adhesive layer (X2) is preferably a layer formed of a pressure-sensitive adhesive composition comprising an energy-ray-curable pressure-sensitive adhesive resin in which a polymerizable functional group is introduced into the side chain as the pressure-sensitive adhesive resin. It is more preferable that it is a layer formed from a pressure-sensitive adhesive composition containing a curable acrylic polymer (B) (hereinafter, also referred to as "acrylic polymer (B)" or "component (B)").

The pressure-sensitive adhesive layer (X2) formed from the pressure-sensitive adhesive composition has an excellent adhesive force capable of sufficiently holding the object to be processed before irradiation with energy rays, but the adhesive strength decreases after irradiation with energy rays. Accordingly, the processed product can be easily separated from the pressure-sensitive adhesive sheet (II).

The content of the component (B) in the pressure-sensitive adhesive composition is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more with respect to the total amount (100% by mass) of the pressure-sensitive adhesive composition. And, preferably, it is 99.9 mass% or less, More preferably, it is 99.0 mass% or less, More preferably, it is 98.0 mass% or less.

The thickness of the pressure-sensitive adhesive layer (X2) is preferably 1 to 100 μm, more preferably 1 to 100 μm, more preferably from the viewpoint of having good adhesion and good followability to an object to be processed having a large difference in surface irregularities, such as a semiconductor wafer having bumps or the like. Preferably, it is 1 to 75 µm, more preferably 1 to 50 µm.

In addition, when the pressure-sensitive adhesive composition as a material for forming the pressure-sensitive adhesive layer (X2) contains an energy-ray-curable pressure-sensitive adhesive resin such as an energy-ray-curable acrylic polymer (B), it is preferable to further contain a crosslinking agent or a photopolymerization initiator. Do.

Examples of the crosslinking agent include those that are the same as those blended in the acrylic resin described above, and the range of the content is also as described above, but the gel fraction of the pressure-sensitive adhesive layer (X2) is increased, and the paste remains in the processed product when the processed product is separated. From the viewpoint of suppressing the occurrence of this, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1.0 to 10 parts by mass per 100 parts by mass of the adhesive resin having a functional group.

As a photoinitiator, the same thing as what is blended in the above-mentioned solvent-free resin composition (y1) is mentioned, and the range of content is also as above-mentioned.

Moreover, you may contain other additives other than these.

Hereinafter, the energy ray-curable acrylic polymer (B) contained in the pressure-sensitive adhesive composition will be described.

((B) component: energy ray-curable acrylic polymer (B))

The energy ray-curable acrylic polymer (B) used in one aspect of the present invention is an acrylic copolymer in which a polymerizable functional group is introduced into the side chain and/or the main chain of the non-energy ray-curable acrylic polymer.

Non-energy ray-curable acrylic polymers are, for example, acrylic polymers having structural units derived from alkyl (meth)acrylates having a linear or branched chain alkyl group, and (meth)acrylates having a cyclic structure. And acrylic polymers having constitutional units described above.

Although the polymerizable functional group is as described above, a (meth)acryloyl group is preferable from the viewpoint of ease of introduction into a non-energy ray-curable acrylic polymer.

The mass average molecular weight (Mw) of the component (B) is preferably 100,000 to 1.5 million, more preferably 200,000 to 1.2 million, more preferably 250,000 to 1 million, still more preferably 300,000 to 90 However, it is more preferably 350,000 to 800,000.

As the component (B), from the viewpoint of making a pressure-sensitive adhesive sheet capable of effectively reducing adhesive strength by irradiation with energy rays, an alkyl (meth)acrylate (b1') having an alkyl group having 1 to 18 carbon atoms (hereinafter, referred to as ``monomer (b1')") derived from a structural unit (b1) and a functional group-containing monomer (b2') (hereinafter also referred to as ``monomer (b2')'') derived from an acrylic copolymer having a structural unit (b2) derived from It is preferable to contain an energy ray-curable acrylic copolymer (B1) obtained by reacting (B0) with a polymerizable compound (Xb), and it is more preferable that it is an energy ray-curable acrylic copolymer (B1).

In addition, the form of the copolymerization of the acrylic copolymer (B0) and (B1) is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.

The content of the acrylic copolymer (B1) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, furthermore, based on the total amount (100% by mass) of the component (B) contained in the pressure-sensitive adhesive composition. It is preferably 90 to 100% by mass, even more preferably 100% by mass.

The number of carbon atoms in the alkyl group of the monomer (b1') is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 8, and even more preferably 1 to 6.

Examples of the monomer (b1') include those exemplified as the above-described monomer (a1'), but butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate is preferable, and butyl (meth)acrylate Is more preferable.

The content of the structural unit (b1) in the acrylic copolymer (B0) is preferably based on the total structural units (100 mass%) of the acrylic copolymer (B0) from the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer to be formed. Is 50 to 99.5% by mass, more preferably 60 to 99% by mass, still more preferably 70 to 98% by mass, and even more preferably 80 to 96% by mass.

Examples of the monomer (b2') include those exemplified as the above-described monomer (a2'), but at least one selected from a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and an epoxy group-containing monomer is preferable, and a hydroxyl group-containing monomer is more It is preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.

The content of the structural unit (b2) in the acrylic copolymer (B0) is preferably 0.5 to 40% by mass, more preferably 1 with respect to the total structural units (100% by mass) of the acrylic copolymer (B0). It is -30 mass%, More preferably, it is 2-25 mass%, More preferably, it is 3-15 mass%.

When the content of the structural unit (b2) is 0.5% by mass or more, the content of the structural unit (b2) having a functional group serving as a reaction point with the polymerizable compound (Xb) can be sufficiently secured, and curability is Since the high pressure-sensitive adhesive layer (X2) can be formed, when peeling the cutting material and/or the grinding material from the pressure-sensitive adhesive layer (X2), the occurrence of the residual of the pressure-sensitive adhesive layer (X2) to the cutting material and/or the grinding material is prevented. It can be peeled off while preventing.

In addition, when the content of the structural unit (b2) is 40% by mass or less, a sufficient pot life can be ensured when forming the pressure-sensitive adhesive layer (X2) by applying the solution of the pressure-sensitive adhesive composition.

In addition, the polymerizable compound (Xb) means a compound having a functional group bondable to a functional group in the constituent unit (b2) of the acrylic copolymer (B0) (hereinafter, also referred to as a "reactive functional group") and a polymerizable functional group.

The acrylic copolymer (B0) may have a structural unit (b3) derived from a monomer (b3') other than the monomers (b1') and (b2').

As other monomer (b3'), what was illustrated as the above-mentioned monomer (a3') is mentioned.

The content of the structural unit (b3) in the acrylic copolymer (B0) is preferably 0 to 20% by mass, more preferably 0 with respect to the total structural units (100% by mass) of the acrylic copolymer (B0). It is 10 mass%, more preferably 0-5 mass%, and even more preferably 0-1 mass%.

In addition, the above-described monomers (b1') to (b3') may be used alone or in combination of two or more.

The energy ray-curable acrylic copolymer (B1) is obtained by reacting the acrylic copolymer (B0) having the above-described structural units (b1) and (b2) with a polymerizable compound (Xb).

Examples of the polymerizable compound (Xb) include those exemplified as the polymerizable compound (Xa) described above, but among these, a compound having a reactive functional group and 1 to 5 polymerizable functional groups per molecule desirable.

As said reactive substituent, an isocyanate group, a carboxyl group, an epoxy group, etc. are mentioned, for example, and an isocyanate group is preferable.

As said polymerizable functional group, as mentioned above, a (meth)acryloyl group, a vinyl group, etc. are mentioned, and a (meth)acryloyl group is preferable.

As a specific polymerizable compound (Xb), (meth)acryloyloxyethyl isocyanate is preferable.

In addition, the polymerizable compound (Xb) may be used alone or in combination of two or more.

In the acrylic copolymer (B1), regarding the relationship between the number of functional groups in the acrylic copolymer (B0) and the blending amount of the polymerizable compound (Xb), while having an appropriate adhesive strength before irradiation with energy rays, after irradiation with energy rays, From the viewpoint of obtaining a pressure-sensitive adhesive sheet whose adhesive strength can be effectively lowered, the value of α calculated from the following formula (1) is preferably 0.5 to 50, more preferably 1.0 to 40, further preferably 1.2 to 35, Even more preferably, it is 1.5-30.

In addition, the value of α corresponds to the number of polymerizable functional groups contained in the acrylic copolymer (B1).

Equation (1): α = [P _B ] × [Q _B ] × [R _B ]/100

(In formula (1), [P _B ] represents the content of the structural unit (b2) with respect to 100 parts by mass of all the structural units of the acrylic copolymer (B0). [Q _B ] is the acrylic copolymer (B0) Represents the equivalent of the polymerizable compound (Xb) with respect to 100 equivalents of the functional group derived from the functional group-containing monomer possessed by [R _B ] represents the number of polymerizable functional groups that the polymerizable compound (Xb) has.)

<Intermediate layer (Z2)>

In one aspect of the present invention, the intermediate layer (Z2) is formed of an intermediate layer-forming composition (z2) containing a non-energy ray-curable acrylic polymer (C) and an energy ray-curable acrylic polymer (D).

By forming the intermediate layer Z2, it becomes the adhesive sheet II excellent in followability with respect to the object to be processed with large surface irregularities, such as a semiconductor wafer having bumps. Therefore, when performing at least any of cutting and grinding on the object to be processed to which the pressure-sensitive adhesive sheet (II) is affixed, while suppressing the damage of the object to be processed, cutting debris, grinding debris, cutting water, grinding water, etc. This can prevent intrusion into the affixed surface of the object to be processed with the adhesive sheet (II).

In addition, the intermediate layer (Z2) may or may not have adhesiveness.

The thickness of the intermediate layer Z2 is appropriately selected depending on the degree of irregularities of the object to be processed, for example, when the object to be processed is a semiconductor wafer or semiconductor chip, the height of the bumps of the semiconductor wafer or semiconductor chip. It is -800 µm, more preferably 15-600 µm, still more preferably 20-400 µm.

When the thickness of the intermediate layer Z2 is 10 µm or more, it is possible to improve the followability to the object to be processed having a large difference in irregularities. On the other hand, when the thickness of the intermediate layer is 800 µm or less, it is easy to suppress the deformation of the pressure-sensitive adhesive sheet (II).

The intermediate layer-forming layer composition (z2), which is a material for forming the intermediate layer (Z2), has good adhesion between the intermediate layer (Z2) of the adhesive sheet (II) and the adhesive layer (X2) after irradiation with energy rays, Alternatively, from the viewpoint of suppressing the breakage of the pressure-sensitive adhesive layer (X2) or the occurrence of residues of the pressure-sensitive adhesive layer (X2) on the surface of the cut and/or the grinding material when the grinding material is peeled from the pressure-sensitive adhesive sheet (II), a specific energy ray Curable acrylic polymer (C) (hereinafter, also referred to as "acrylic polymer (C)" or "component (C)"), and energy ray-curable acrylic polymer (D) having a mass average molecular weight of 50,000 to 250,000 (hereinafter , It is preferable to contain "acrylic polymer (D)" or "(D) component").

In addition, from the viewpoint of further improving the adhesion between the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays, the content of the component (D) in the composition for forming an intermediate layer (z2) is (C) component 100 With respect to mass parts, it is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 37 parts by mass or more, and even more preferably 40 parts by mass or more.

In addition, in one aspect of the present invention, from the viewpoint of suppressing leaching of a part of the intermediate layer (Z2) from the end of the pressure-sensitive adhesive sheet (II), the content of the component (D) in the composition for forming an intermediate layer (z2) is (C ) Based on 100 parts by mass of the component, it is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, and still more preferably 130 parts by mass or less.

The total content of the component (C) and the component (D) in the composition for forming an intermediate layer (z2) is preferably 70% by mass or more, more preferably, based on the total amount (100% by mass) of the composition for forming an intermediate layer (z2). Preferably, it is 80 mass% or more, more preferably 90 mass% or more, more preferably 99.9 mass% or less, more preferably 99.0 mass% or less, still more preferably 98.0 mass% or less.

Moreover, it is preferable that the composition for intermediate layer formation (z2) further contains a photoinitiator and a crosslinking agent in addition to the said (C) component and (D) component. Moreover, you may contain other additives other than these.

Examples of the crosslinking agent include those which are the same as those blended in the acrylic resin described above, and the range of the content is also as described above.

As a photoinitiator, the same thing as what is blended in the above-mentioned solvent-free resin composition (y1) is mentioned, and the range of content is also as above-mentioned.

Moreover, you may contain other additives other than these.

Hereinafter, the non-energy ray-curable acrylic polymer (C) and the energy ray-curable acrylic polymer (D) contained in the intermediate layer-forming composition (z2) will be described.

((C) component: non-energy ray-curable acrylic polymer (C))

As the non-energy ray-curable acrylic polymer (C), for example, a polymer having a structural unit derived from an alkyl (meth)acrylate having a linear or branched alkyl group, and a (meth)acrylate having a cyclic structure And polymers having a structural unit derived from.

The mass average molecular weight (Mw) of the component (C) is preferably 300,000 to 1.5 million, more preferably 350,000 to 1.3 million, more preferably 400,000 to 1.2 million, still more preferably 400,000 to 110. However, more preferably, they are 450,000 to 900,000.

As the component (C), from the viewpoint of compatibility with the component (D), an alkyl (meth)acrylate (c1') having an alkyl group having 1 to 18 carbon atoms (hereinafter, also referred to as "monomer (c1')") It is preferable to include an acrylic copolymer (C1) having a structural unit (c2) derived from the derived structural unit (c1) and a functional group-containing monomer (c2') (hereinafter also referred to as ``monomer (c2')''), , It is more preferable that it is an acrylic copolymer (C1).

In addition, the form of the copolymerization of the acrylic copolymer (C1) is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.

The content of the acrylic copolymer (C1) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount (100% by mass) of the component (C) contained in the intermediate layer-forming composition (z2). It is 100 mass%, more preferably 90 to 100 mass%, and even more preferably 100 mass%.

The number of carbon atoms in the alkyl group of the monomer (c1') is more preferably 4 to 12, still more preferably 4 to 8, and even more preferably 4 to 6 from the viewpoint of compatibility with the component (D).

As the monomer (c1'), the same thing as the above-mentioned monomer (a1') is mentioned.

Among these, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable, and butyl (meth)acrylate is more preferable.

The content of the structural unit (c1) in the acrylic copolymer (C1) is preferably 50 to 99.5% by mass, more preferably 60, based on the total structural units (100% by mass) of the acrylic copolymer (C1). It is -99 mass%, More preferably, it is 70-95 mass%, More preferably, it is 80-93 mass%.

When the content of the structural unit (c1) is 50% by mass or more, it is preferable because it is possible to obtain a pressure-sensitive adhesive sheet having good followability with respect to an object having a large difference in irregularities.

Moreover, if the content of the structural unit (c1) is 99.5% by mass or less, it is preferable because the content of the structural unit (c2) can be sufficiently secured and compatibility with the component (D) can be improved.

In addition, the acrylic copolymer (C1) is an alkyl group having an alkyl group having 4 or more carbon atoms (preferably 4 to 12, more preferably 4 to 8, still more preferably 4 to 6) as the structural unit (c1) ( It is preferable to have a structural unit (c11) derived from meth)acrylate.

The content ratio of the structural unit (c11) in the structural unit (c1) is preferably 60% by mass or more, more preferably, based on the total amount (100% by mass) of the structural unit (c1) of the acrylic copolymer (C1). Preferably, it is 70 mass% or more, more preferably 80 mass% or more, even more preferably 85 mass% or more, and preferably 100 mass% or less.

As the functional group which the monomer (c2') has, the same functional group as the functional group of the above-described monomer (a2') can be mentioned.

Also about the specific monomer (c2'), the thing similar to the above-mentioned monomer (a2') is mentioned.

Among these, at least one selected from a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and an epoxy group-containing monomer is preferable, and a carboxyl group-containing monomer is more preferable.

The specific examples of the hydroxyl group-containing monomer, the carboxyl group-containing monomer, and the epoxy group-containing monomer are also the same as those of the above-described monomer (a2').

The content of the structural unit (c2) in the acrylic copolymer (C1) is preferably 0.5 to 50% by mass, more preferably 1 with respect to the total structural units (100% by mass) of the acrylic copolymer (C1). It is -40 mass%, More preferably, it is 5-30 mass%, More preferably, it is 7-20 mass%.

When the content of the structural unit (c2) is 0.5% by mass or more, it is preferable because compatibility with the component (D) can be improved.

Moreover, when the content of the structural unit (c2) is 50% by mass or less, it is preferable because it can be a pressure-sensitive adhesive sheet having good followability to an adherend having a large difference in irregularities.

The acrylic copolymer (C1) may have a structural unit (c3) derived from a monomer (c3') other than the monomers (c1') and (c2').

As another monomer (c3'), the same thing as the above-mentioned monomer (a3') is mentioned.

The content of the structural unit (c3) in the acrylic copolymer (C1) is preferably 0 to 30% by mass, more preferably 0 with respect to the total structural units (100% by mass) of the acrylic copolymer (C1). It is 20 mass%, more preferably 0-10 mass%, and even more preferably 0-5 mass%.

In addition, the above-described monomers (c1') to (c3') may be used alone or in combination of two or more.

((D) component: energy ray-curable acrylic polymer (D))

The energy ray-curable acrylic polymer (D) is an acrylic polymer into which a polymerizable functional group is introduced with respect to a non-energy ray-curable acrylic polymer.

Further, the polymerizable functional group is introduced into the main chain and/or the side chain of the non-energy ray-curable acrylic polymer.

By containing the component (D) in the intermediate layer, when irradiated with energy rays, the component (D) and the component (B) in the pressure-sensitive adhesive layer (X2) react and bond, and the intermediate layer (Z2) of the pressure-sensitive adhesive sheet (II) and the pressure-sensitive adhesive It is thought that the adhesiveness of the layer (X2) improves. Moreover, it is thought that the adhesive layer (X2) and the intermediate layer (Z2) become hard, and the residual of the paste can be suppressed. Therefore, it is possible to suppress residual adhesion of the pressure-sensitive adhesive layer (X2) at the time of peeling of the cut material and/or the grinding material from the pressure-sensitive adhesive sheet (II).

As a non-energy ray-curable acrylic polymer, an acrylic polymer having a structural unit derived from an alkyl (meth)acrylate having a linear or branched chain alkyl group, or a constitution derived from a (meth)acrylate having a cyclic structure And an acrylic polymer having a unit.

The polymerizable functional group may be a group containing an energy ray polymerizable carbon-carbon double bond, and examples thereof include a (meth)acryloyl group, a vinyl group, etc., but the viewpoint of easy introduction of an energy ray polymerization group In, (meth)acryloyl group is preferable.

Further, the energy ray polymerizable group may be bonded to the main chain or side chain of the non-energy ray-curable acrylic polymer via an alkylene group, an alkyleneoxy group, a polyalkyleneoxy group, or the like.

The mass average molecular weight (Mw) of the component (D) is preferably 50,000 to 250,000, more preferably 60,000 to 220,000, still more preferably 70,000 to 200,000, even more preferably 80,000 It is 180,000 to 180,000, further preferably, it is 8.5 to 150,000.

When Mw of the component (D) is less than 50,000, the stability over time of the obtained pressure-sensitive adhesive sheet is likely to be deteriorated. In short, when the pressure-sensitive adhesive sheet is stored for a long time, part of the component (D) migrates into the pressure-sensitive adhesive layer, and the adhesive strength of the pressure-sensitive adhesive sheet becomes unstable, and after irradiation with energy rays, the pressure-sensitive adhesive layer (X2) is excessively cured. easy. As a result, when the PSA sheet is used after long-term storage, or when the object is left affixed for a long period of time, the adhesion between the intermediate layer (Z2) and the PSA layer (X2) after irradiation with energy rays becomes insufficient. For this reason, when peeling off the said adhesive sheet, the residue of the adhesive layer (X2) may adhere to the fracture|rupture of the adhesive layer (X2), a cut product, and/or a grinding product.

On the other hand, when the Mw of the component (D) exceeds 250,000, the adhesion between the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays tends to be poor, and the cutting and grinding material are peeled from the pressure-sensitive adhesive sheet (II). In this case, there are cases where the residue of the pressure-sensitive adhesive layer (X2) adheres to the breakage of the pressure-sensitive adhesive layer (X2) or the cut and/or grinding material.

As the component (D), from the viewpoint of making a pressure-sensitive adhesive sheet excellent in stability over time, and from the viewpoint of making a pressure-sensitive adhesive sheet having improved adhesion between the formed intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays. , A structural unit (d1) derived from an alkyl (meth)acrylate (d1') having an alkyl group having 1 to 18 carbon atoms (hereinafter also referred to as ``monomer (d1')'') and a functional group-containing monomer (d2') (hereinafter , An acrylic copolymer (D0) having a structural unit (d2) derived from (also referred to as "monomer (d2')") and an energy ray-curable acrylic copolymer (D1) obtained by reacting a polymerizable compound (Xd) It is preferable to include, and it is more preferable that it is an energy ray-curable acrylic copolymer (D1).

Further, the form of the copolymerization of the acrylic copolymers (D0) and (D1) is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.

The content of the acrylic copolymer (D1) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount (100% by mass) of the component (D) contained in the intermediate layer-forming composition (z2). It is 100 mass%, more preferably 90 to 100 mass%, and even more preferably 100 mass%.

The number of carbon atoms in the alkyl group of the monomer (d1') is more preferably 4 to 12, still more preferably 4 to 8, and even more preferably 4 to 6.

Examples of the monomer (d1') include those illustrated as the above-described monomer (a1').

Among these, butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate is preferable, and butyl (meth)acrylate is more preferable.

The content of the structural unit (d1) in the acrylic copolymer (D0) is preferably 50 to 99% by mass, more preferably 55 with respect to the total structural units (100% by mass) of the acrylic copolymer (D0). It is -95 mass%, More preferably, it is 60-90 mass%, More preferably, it is 65-85 mass%.

When the content of the structural unit (d1) is 50% by mass or more, it is preferable because the shape of the intermediate layer (Z2) to be formed can be sufficiently maintained.

Moreover, if the content of the structural unit (d1) is 99% by mass or less, the content of the structural unit (d2) having a functional group serving as a reaction point with the polymerizable compound (Xd) can be sufficiently secured, and the intermediate layer (Z2) to be formed It is preferable because the adhesiveness after energy ray irradiation of the over-adhesive layer (X2) can be improved.

Examples of the monomer (d2') include those exemplified as the above-described monomer (a2'), but at least one selected from a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and an epoxy group-containing monomer is preferable, and a hydroxyl group-containing monomer is more It is preferable, hydroxyacryl (meth)acrylate is more preferable, and 2-hydroxyethyl (meth)acrylate is even more preferable.

The content of the structural unit (d2) in the acrylic copolymer (D0) is preferably 1 to 50% by mass, more preferably 5, based on the total structural units (100% by mass) of the acrylic copolymer (D0). It is -45 mass %, More preferably, it is 10 to 40 mass %, More preferably, it is 15 to 35 mass %.

When the content of the constituent unit (d2) is 1% by mass or more, a sufficient reaction point with the polymerizable compound (Xd) can be secured in order to improve the adhesion between the formed intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays. It is preferable because there is.

Moreover, when the content of the structural unit (d2) is 50 mass% or less, it is preferable because the shape of the intermediate layer (Z2) to be formed can be sufficiently maintained.

The acrylic copolymer (D0) may have a structural unit (b3) derived from a monomer (d3') other than the monomers (d1') and (d2').

As another monomer (d3'), what was illustrated as the above-mentioned monomer (a3') is mentioned.

The content of the structural unit (d3) in the acrylic copolymer (D0) is preferably 0 to 30% by mass, more preferably 0 with respect to the total structural units (100% by mass) of the acrylic copolymer (D0). It is 20 mass%, more preferably 0-10 mass%, and even more preferably 0-5 mass%.

In addition, the above-described monomers (d1') to (d3') may be used alone or in combination of two or more.

In the energy ray-curable acrylic copolymer (D1), the functional group in the structural unit (d2) of this acrylic copolymer (D0) is reacted with the polymerizable compound (Xd), and the polymerizable functional group possessed by the polymerizable compound (Xd) A is introduced into at least one of the main chain and side chain of the acrylic copolymer (D0).

The polymerizable compound (Xd) is a compound having a polymerizable functional group and is not particularly limited as long as it is a compound having a reactive functional group.

Moreover, it is preferable that it is a compound which has the said reactive substituent and has 1-5 polymerizable functional groups per molecule among polymerizable compounds (Xd).

As said reactive substituent, an isocyanate group, a carboxyl group, an epoxy group, etc. are mentioned, for example, and an isocyanate group is preferable.

As said polymerizable functional group, as mentioned above, a (meth)acryloyl group, a vinyl group, etc. are mentioned, and a (meth)acryloyl group is preferable.

As a specific polymerizable compound (Xd), the same compound as the polymerizable compound (Xb) mentioned above is mentioned.

The polymerizable compound (Xd) may be used alone or in combination of two or more.

Among these, (meth)acryloyloxyethyl isocyanate is preferable from the viewpoint of a compound having an isocyanate group preferable as the reactive substituent and having an appropriate distance between the acrylic copolymer (D0) and the energy ray polymerizable group.

In the acrylic copolymer (D1), with respect to the relationship between the number of functional groups in the acrylic copolymer (D0) and the blending amount of the polymerizable compound (Xd), the intermediate layer (Z2) to be formed and the pressure-sensitive adhesive layer (X2) after energy ray irradiation From the viewpoint of improving adhesion, the value of β calculated from the following formula (2) is preferably 1 to 50, more preferably 2 to 40, still more preferably 3 to 35, and even more preferably 5 to It is 30.

In addition, the value of β corresponds to the number of energy ray polymerizable groups in the acrylic copolymer (D1).

Equation (2): β = [P _d ] × [Q _d ] × [R _d ]/100

(Formula (2) of, [P _d] shows the content of the constituent unit (d2) with respect to 100 parts by mass of all the structural units of the acrylic copolymer (D0). [Q _d], the acrylic copolymer (D0) Represents the equivalent of the polymerizable compound (Xd) with respect to 100 equivalents of the functional group derived from the functional group-containing monomer possessed by [R _d ] represents the number of polymerizable functional groups contained in the polymerizable compound (Xd).)

(Other additives contained in the composition for forming an intermediate layer)

In the intermediate layer forming composition (z2), other additives may be contained within a range that does not impair the effects of the present invention.

Other additives include, for example, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, tackifiers, and the like.

When these additives are contained, the content of each additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass per 100 parts by mass of the component (A).

<Park Lee Jae>

In the adhesive laminate of one aspect of the present invention, a release material may be further laminated on the surfaces of the pressure-sensitive adhesive layers (X1) and (X2) to be adhered to the object to be processed.

As the release material, a release sheet subjected to a double-sided release treatment, a release sheet subjected to a single-sided release treatment, and the like are used, and the release agent may be applied onto a substrate for a release material.

Examples of the substrate for a release material include papers such as high-quality paper, glassine paper, and kraft paper; Plastic films such as polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin, and olefin resin films such as polypropylene resin and polyethylene resin; And the like.

Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

The thickness of the release material is not particularly limited, but is preferably 10 to 200 µm, more preferably 25 to 170 µm, and still more preferably 35 to 80 µm.

<Physical properties of adhesive sheet (II)>

In one aspect of the present invention, from the viewpoint of making it easier to perform cutting and grinding in the step (4), the pressure-sensitive adhesive sheet (II) satisfies one or more of the following requirements (α) to (γ). It is preferable, and it is more preferable to satisfy any two of the following requirements (α) to (γ), and even more preferably to satisfy all of the requirements (α) to (γ).

-Requirement (α): The Young's modulus of the substrate (Y2) is 1.0 MPa or more.

-Requirement (β): The thickness of the substrate (Y2) is 5 µm or more.

Requirement (γ): The storage modulus G'(23°C) of the pressure-sensitive adhesive layer (X2) is 0.10 MPa or more.

In addition, from the viewpoint of making it easier to perform cutting and grinding in the step (4), the Young's modulus of the base material (Y2) specified in the requirement (α) is preferably 1.0 to 1000 MPa, and 1.5 to 800 MPa. It is more preferable and it is still more preferable that it is 2.0-500 MPa.

In addition, from the viewpoint of making it easier to perform cutting and grinding in the step (4), the thickness of the substrate (Y2) specified in the requirement (β) is preferably 5 to 250 µm, and 10 to 230 µm. It is more preferable and it is still more preferable that it is 20-210 micrometers.

In addition, from the viewpoint of making it easier to perform cutting and grinding in step (4), the storage elastic modulus G'(23°C) of the pressure-sensitive adhesive layer (X2) specified in the requirement (γ) is preferably 0.10 to 1 MPa. And, it is more preferable that it is 0.12 to 0.9 MPa, and it is still more preferable that it is 0.14 to 0.8 MPa.

[Each process of manufacturing method of processed product]

Next, each step of the method for manufacturing a processed product of the present invention will be described in detail.

The manufacturing method of the processed article of this invention has a base material (Y1) and an adhesive layer (X1), and the thermally expandable adhesive sheet (I) containing thermally expandable particles of the thermal expansion initiation temperature (t) in any layer, and the base material ( Cutting and grinding using an adhesive laminate comprising an adhesive sheet (II) having Y2) and an adhesive layer (X2), and directly laminating the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) As a method of manufacturing a processed product subjected to at least any of the processing,

Having the following steps (1) to (3) in this order,

Process (1): a step of affixing the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and affixing the object to be processed on the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate

Process (2): A process of performing one or more processing on the object to be processed

Step (3): The adhesiveness while maintaining a state in which the object to be processed is affixed to the surface of the adhesive layer (X2) of the adhesive laminate by heating at or above the thermal expansion initiation temperature (t) of the thermally expandable particles. Step of separating the laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II)

In addition, it has the following process (4),

Step (4): A step of performing at least one of cutting and grinding on the surface of the object to be processed on the side opposite to the affixed surface with the adhesive layer (X2)

The said process (4) is implemented in at least any one of following (X) and (Y).

(X): As the one or more processing, it is carried out in the step (2).

(Y): It is implemented after the said process (3)

In the production method of the present invention, the above-described adhesive laminate is used. Specifically, while affixing the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate to the support, the object to be processed is formed on the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate. Attach it to use. Therefore, predetermined processing can be performed while the object to be processed is fixed to the support. In addition, after performing the predetermined processing, the pressure-sensitive adhesive sheet (II) on which the object to be processed, which has been subjected to the predetermined processing, is affixed can be easily removed collectively from the pressure-sensitive adhesive sheet (I) with a slight force. In short, the pressure-sensitive adhesive sheet (II) on which the object to be processed that has undergone the predetermined processing is affixed can be easily separated from the support. Therefore, it is possible to provide the object to be processed, which has been subjected to the predetermined processing, to the next step without affixing it to a new adhesive sheet.

Hereinafter, each step of the manufacturing method of the present invention will be described with appropriate reference to FIGS. 4 and 5.

<Step (1)>

4(a) and 5(a) are cross-sectional schematic diagrams showing a state in which an object to be processed is affixed to a support through an adhesive laminate.

In step (1), as shown in Figs. 4 (a) and 5 (a), through the adhesive laminate 1a of the first aspect, the object to be processed 60, 70 is provided to the support 50. After affixing, the support, the adhesive laminate, and the object to be processed are laminated in this order.

In addition, in Figs. 4 and 5, an example in which the adhesive laminate 1a shown in Fig. 1(a) is used is shown, but also in the case of using the adhesive laminate of the present invention having a different configuration, similarly, The support, the adhesive laminate, and the object to be processed are laminated in this order.

4(a) and 5(a), in the step (1), the object to be processed 60, 70 is affixed to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate. , The pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the adhesive laminate and the support 50 are affixed.

Further, examples of the object to be processed to be affixed to the adhesive laminate include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and panel substrates.

In addition, the object to be processed may be a semiconductor wafer or the like in which the cut grooves are formed on the surface, and the side of the formation surface of the cut grooves may be bonded to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II). Further, the object to be processed may be a semiconductor wafer or the like in which a modified region has been previously formed therein by irradiation with laser light. In these cases, by grinding in the step (4), the cut groove or the modified region becomes the starting point for division, and the object to be processed can be divided.

That is, when the object to be processed is a semiconductor wafer having cutout grooves formed on the surface, in the manufacturing method of one aspect of the present invention, the step (1) is the following step (1-C), and the step (4) is the following step ( 4-C).

Step (1-C): A surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate is affixed to the support, and the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive laminate has a cutout groove of the semiconductor wafer Process of attaching

Process (4-C): A process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2)

In addition, when the object to be processed is a semiconductor wafer having a modified region serving as a division starting point, in the manufacturing method of one aspect of the present invention, the step (4) is the following step (4-A).

Process (4-A): The process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2)

The support is used in order to fix the object to be processed in step (2) and to increase the precision of processing.

It is preferable that the said support is affixed to the whole surface of the adhesive surface of the adhesive layer (X1) of an adhesive laminated body.

Therefore, it is preferable that the support body has a plate shape. In addition, as shown in FIGS. 4 and 5, the area of the surface of the adhesive surface 122a of the adhesive layer (X1) and the surface of the support body 50 on the affixed side is of the adhesive surface (122a) of the adhesive layer (X1). It is preferable that it is more than an area.

As the material constituting the support, depending on the type of the object to be processed or the processing performed in the step (2), it is appropriately selected after considering characteristics requiring mechanical strength and heat resistance.

As a material constituting a specific support, for example, a metal material such as SUS; Non-metallic inorganic materials such as glass and silicon wafers; Resin materials such as epoxy resin, ABS resin, acrylic resin, engineering plastic, super engineering plastic, polyimide resin, and polyamideimide resin; And composite materials such as glass epoxy resins, and among them, SUS, glass, and silicon wafers are preferred.

Further, examples of engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).

Examples of super engineering plastics include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).

The thickness of the support is appropriately selected in consideration of required characteristics and the like, but is preferably 20 µm or more and 50 mm or less, and more preferably 60 µm or more and 20 mm or less.

The temperature conditions in the step (1) may be less than the expansion start temperature (t) of the thermally expandable particles.

<Step (2)>

In step (2), one or more processing is performed on the object to be processed, which is affixed to the pressure-sensitive adhesive layer (X2) of the adhesive laminate of the present invention in step (1).

The processing treatment performed in the step (2) includes, for example, a sealing treatment using a resin for the object to be processed, a treatment for forming a modified region serving as a division starting point in the object to be processed, a circuit formation treatment, an etching treatment, a plating treatment, and A sputtering treatment, a vapor deposition treatment, a protective film formation treatment, and a lamination treatment using a separately prepared pressure-sensitive adhesive sheet may be mentioned.

In addition, the machining treatment performed in the step (2) may be at least any machining treatment of cutting and grinding on the object to be processed.

That is, the machining treatment performed in step (2) may be a machining that includes at least any of the steps of cutting the object to be processed and the step of grinding, or even if it does not include the step of cutting the object to be processed and the step of grinding. do.

The temperature conditions in step (2) may also be less than the expansion start temperature (t) of the thermally expandable particles, similarly to the step (1).

Hereinafter, as step (2), when performing a treatment (step (2-A)) of forming a modified region serving as a division starting point in an object to be processed, sealing treatment using a resin for the object to be processed (step (2-B) ) Will be described as an example.

(Step (2-A))

Step (2-A) is a step in which the object to be processed is a semiconductor wafer, and a modified region serving as a division starting point is formed on the semiconductor wafer.

Specifically, as shown in Fig. 4(b), the surface of the semiconductor wafer opposite to the affixed surface of the pressure-sensitive adhesive sheet (II) is the laser light incident surface, and the laser light so that the condensing point of the laser light is inside the semiconductor wafer. By irradiation, a modified region 71 due to multiphoton absorption or the like is formed. The modified region 71 functions as a starting point for dividing the semiconductor wafer by grinding in the step (4).

In addition, in the manufacturing example shown in FIG. 4, the process (4) is performed after the process (3), but after the process (2-A), the process (4) is one of one or more processes in the process (2). You may make it grind. In this case, without separating the semiconductor wafer into pieces from the pressure-sensitive adhesive sheet (II), the pieced semiconductor wafer can be provided to the next step while affixed to the pressure-sensitive adhesive sheet (II).

That is, in the manufacturing method of one aspect of the present invention, the object to be processed is a semiconductor wafer, and at least one processing in the step (2) includes the following step (2-A),

Process (2-A): A process of forming a modified region serving as a division starting point on the semiconductor wafer

Step (4) is the following step (4-A),

Process (4-A): The process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2)

Step (4-A) is implemented in the following (X-A) or (Y-A).

(X-A): One or more processing is performed after step (2-A)

(Y-A): Implemented after step (3)

(Step (2-B))

In step (2-B), the object to be processed is a semiconductor chip, and among the adhesion surfaces of the semiconductor chip and the pressure-sensitive adhesive layer (X2), the peripheral portion of the semiconductor chip is covered with a sealing material, and the sealing material is cured, This is a step of obtaining a cured encapsulant obtained by encapsulating a semiconductor chip in a cured encapsulant.

As shown in FIG. 5, when the manufacturing method of the present invention has the step (2-B), in the step (1), the semiconductor chip 60 is used as the object to be processed.

As the semiconductor chip 60, a conventionally known one can be used, and an integrated circuit composed of circuit elements such as a transistor, a resistor, and a capacitor is formed on the circuit surface.

And it is preferable to mount so that the circuit surface of the semiconductor chip 60 may be covered by the adhesive surface of the adhesive layer (X2) of the adhesive sheet (II). For mounting the semiconductor chip, known devices such as a flip chip bonder and a die bonder can be used.

The layout of the arrangement of the semiconductor chips 60, the number of arrangements, etc. may be appropriately determined according to the shape of the target package and the number of productions.

Here, in the manufacturing method of one aspect of the present invention, the semiconductor chip 60 is covered with an encapsulant in a region larger than the chip size, such as FOWLP and FOPLP, and not only the circuit surface of the semiconductor chip 60 but also the encapsulant Also in the surface area, it is preferably applied to a package forming a redistribution layer.

Therefore, the semiconductor chip 60 is placed on a part of the adhesive surface of the adhesive layer X2, and a plurality of semiconductor chips 60 are placed on the adhesive surface in a state that is aligned at regular intervals. It is preferable that the plurality of semiconductor chips 60 are placed on the adhesive surface in a state in which a plurality of semiconductor chips 60 are arranged in a matrix form of a plurality of rows and columns at regular intervals.

The spacing between the semiconductor chips 60 may be appropriately determined in accordance with the shape of the intended package or the like.

And in step (2-B), the adhesive surface of the said semiconductor chip 60 and the adhesive layer (X1) of at least the peripheral part of the said semiconductor chip 60 is covered with a sealing material (hereinafter, also referred to as a ``coating step''). Then) the said sealing material is hardened, and the hardened sealing body 61 obtained by sealing the said semiconductor chip 60 by the hardening sealing material is obtained (it is also called "hardening process" hereafter).

By placing the semiconductor chip 60 on a part of the adhesive surface of the adhesive layer (X2), a peripheral portion of the semiconductor chip 60 is formed in the adhesive surface of the adhesive layer (X2).

In short, the peripheral portion of the semiconductor chip 60 refers to the adhesive surface of the pressure-sensitive adhesive layer X2 corresponding to the gap between the adjacent semiconductor chips 60 among the plurality of semiconductor chips 60.

In the covering step of step (2-B), first, among the adhesive surfaces of the semiconductor chip 60 and the adhesive layer X2, the peripheral portion of the semiconductor chip 60 is covered with a sealing material. The sealing material is also filled in the gap between the plurality of semiconductor chips CP while covering the entire surface of the semiconductor chip CP.

The encapsulant has a function of protecting the semiconductor chip CP and an element accompanying it from an external environment.

Examples of the sealing material include a sealing material containing a thermosetting resin and a sealing material containing an energy ray-curable resin that can be appropriately selected and used from among those used as a semiconductor sealing material. .

Further, the sealing material may be a solid material such as granular or sheet form at room temperature, or may be a liquid form in the form of a composition, but a sheet-like sealing material is preferable from the viewpoint of workability.

As a method of covering the semiconductor chip 60 and its periphery using an encapsulant, it can be appropriately selected and applied according to the type of encapsulant from among methods conventionally applied to the semiconductor encapsulation process, for example, A roll lamination method, a vacuum press method, a vacuum lamination method, a spin coating method, a die coating method, a transfer molding method, a compression molding method, and the like can be applied.

And after performing the coating process, the sealing material is hardened, and the hardened sealing body 61 obtained by sealing the semiconductor chip 60 by the hard sealing material can be obtained.

In addition, it is preferable that the coating step and the curing step of the step (2-B) are performed under a temperature condition of less than the expansion start temperature (t) of the thermally expandable particles.

Moreover, although the coating process and the curing process may be performed separately, when heating the sealing material in the coating process, the sealing material may be cured as it is by the heating, and the coating process and the curing process may be simultaneously performed.

In addition, in the manufacturing example shown in FIG. 5, the process (4) is performed after the process (3), but after the process (2-B), the process (4) is one of one or more processes in the process (2). You may do it. In this case, the cured encapsulant can be provided to the next step without separating the cured encapsulant from the adhesive sheet (II), while the cured encapsulant is affixed to the adhesive sheet (II).

That is, in the manufacturing method of one aspect of the present invention, the object to be processed is a semiconductor chip, and at least one processing in the step (2) includes the following step (2-B),

Process (2-B): of the adhesive surfaces of the semiconductor chip and the pressure-sensitive adhesive layer (X2), the periphery of the semiconductor chip is covered with a sealing material, the sealing material is cured, and the semiconductor chip is applied to the cured sealing material. Process of obtaining a cured sealing body formed by sealing

Step (4) is implemented in at least any one of the following (X-B) and (Y-B).

(X-B): The one or more processing is performed after the step (2-B)

(Y-B): It is carried out after the above step (3)

<Step (3)>

In step (3), the interface between the adhesive sheet (I) of the adhesive laminate and the substrate (Y2) of the adhesive sheet (II) by heat treatment (heat treatment for separation) at a temperature equal to or higher than the expansion start temperature (t) Separated from P.

4(c) and 5(c) are cross-sectional schematic diagrams showing a state separated at the interface P by the separation heat treatment.

4(c) and 5(c) show a state in which the object to be processed, which has been subjected to a predetermined processing, is laminated on the pressure-sensitive adhesive sheet II by the heat treatment for separation and separated.

The "expansion initiation temperature (t) or higher temperature" in the heat treatment for separation in the step (3) is equal to or higher than the "expansion initiation temperature (t) + 10°C" and not more than the "expansion initiation temperature (t) + 60°C" It is preferable, and it is more preferable that it is "expansion initiation temperature (t) + 15 degreeC" or more and "expansion initiation temperature (t) + 40 degreeC" or less.

In this way, since the adhesive sheet (II) can be separated from the adhesive sheet (I) and separated from the support body in a state in which the object to be processed, which has been subjected to the predetermined processing in the step (2), is stacked (attached). The operation of affixing the object to be processed later to the pressure-sensitive adhesive sheet can be omitted, and the process can be provided.

<Step (4)>

In step (4), at least any one of cutting and grinding is performed on the surface of the object to be processed on the side opposite to the affixed surface with the adhesive layer (X2).

For example, by cutting the object to be processed, the object to be processed can be divided into a desired size. Moreover, by performing grinding, the object to be processed can be adjusted to a desired thickness. Moreover, it is also possible to perform both cutting and grinding, and to divide the object to be processed and adjust the thickness.

In addition, for example, as shown in Fig. 4(d), by grinding the surface of the semiconductor wafer on the side opposite to the affixed surface of the adhesive sheet (II) of the semiconductor wafer in which the modified region serving as the division starting point is formed by laser light irradiation The semiconductor wafer is divided into a predetermined size by thinning the semiconductor wafer to make it easy to be split, and then generating a gap 72 using the modified region 71 as a division starting point under a processing pressure such as a grinding grindstone. Thus, it can be set as a semiconductor chip.

In addition, as shown in Fig. 5(d), by cutting the coin sealing body 61, a piece 61a of the coin sealing body in which the coin sealing body 61 is divided in units of semiconductor chips (CP) is obtained. I can. The cutting method for separating the hardened sealing body 61 into pieces is not particularly limited, and examples thereof include cutting means such as a dicing saw.

Further, although not shown, the cured encapsulant 61 may be ground for the purpose of exposing the circuit surface of the semiconductor chip.

Moreover, you may have another process further between processes (1)-(4), before process (1), and after process (4). For example, you may have a rewiring formation process, etc.

In addition, step (4) may be performed as one of one or more processing in step (2) as described above, or may be performed after step (3). Furthermore, the process (4) may be carried out as one of one or more processing in the process (2) and after the process (3).

For example, as one of one or more processing in step (2), grinding is performed on the surface of the object to be processed on the opposite side to the affixed surface of the adhesive layer (X2), and cutting is performed after step (3). It is also possible to do.

In addition, as one of the one or more processing in step (2), in one direction of the surface opposite to the affixing surface of the object to be processed with the adhesive layer (X2) (for example, the X-axis direction of the XY plane of the object to be processed) After the process (3), cutting is performed only in the other direction (e.g., the Y-axis direction of the XY plane of the object to be processed) to divide the object to be processed into strips. The object to be processed may be further finely divided (for example, in a square shape).

Example

Although the present invention is specifically described by the following examples, the present invention is not limited to the following examples. In addition, the physical property values in the following Production Examples and Examples are values measured by the following method.

<Mass average molecular weight (Mw)>

Using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, product name "HLC-8020"), it was measured under the following conditions, and the value measured in terms of standard polystyrene was used.

(Measuring conditions)

Column: ``TSK guard column HXL-L'' ``TSK gel G2500HXL'' ``TSK gel G2000HXL'' and ``TSK gel G1000HXL'' (all manufactured by Tosoh Corporation) in sequence

·Column temperature: 40 ℃

·Development solvent: tetrahydrofuran

·Flow rate: 1.0 ml/min

<Measurement of the thickness of each layer>

It measured using a static pressure thickness measuring device (model number: "PG-02J", standard standard: JIS K6783, Z1702, and Z1709 compliant) manufactured by Techrak Co., Ltd.

<Average particle diameter of thermally expandable particles (D ₅₀ ), 90% particle diameter (D ₉₀ )>

The particle distribution of the thermally expandable particles before expansion at 23°C was measured using a laser diffraction type particle size distribution measuring device (for example, the product name "Mastersizer 3000" manufactured by Malvern).

And the particle diameters corresponding to the cumulative volume frequency of 50% and 90% calculated from the smaller particle diameter of the particle distribution, respectively, "average particle diameter of thermally expandable particles (D ₅₀ )" and "90% particle diameter of thermally expandable particles ( D ₉₀ )".

<Storage modulus E'of the thermally expandable base layer (Y1-1)>

The formed thermally expandable base layer (Y1-1) was set to have a size of 5 mm in length × 30 mm in width × 200 µm in thickness, and the release material was removed as a test sample.

Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), the test start temperature is 0°C, the test end temperature is 300°C, the temperature rise rate is 3°C/min, the frequency is 1 Hz, and the amplitude is 20 μm. The storage modulus E'of the test sample at a temperature of was measured.

<Storage shear modulus G'of the first adhesive layer (X11), the second adhesive layer (X12), and the adhesive layer (X2)>

The formed 1st adhesive layer (X11), the 2nd adhesive layer (X12), and the adhesive layer (X2) were cut into a circular shape with a diameter of 8 mm, and the peeling material was removed, overlapped, and the thickness was 3 mm. It was set as a test sample.

Using a viscoelasticity measuring device (manufactured by Anton Paar, device name "MCR300"), under conditions of a test start temperature of 0°C, a test end temperature of 300°C, a temperature increase rate of 3°C/min, and a frequency of 1 Hz, by a torsional shear method, The storage shear modulus G'of the test sample at a predetermined temperature was measured.

<Probe tack value>

The base material to be measured was cut into a square having 10 mm on one side, and then stopped still in an environment of 23°C and 50% RH (relative humidity) for 24 hours as a test sample.

In an environment of 23°C and 50% RH (relative humidity), using a tacking tester (manufactured by Nippon Special Instruments Co., Ltd., product name "NTS-4800"), the probe tack value on the surface of the test sample was determined in JIS Z0237: 1991. It was measured according to.

Specifically, a probe made of stainless steel having a diameter of 5 mm is brought into contact with the surface of the test sample for 1 second with a contact load of 0.98 N/cm 2, and then the probe is separated from the surface of the test sample at a rate of 10 mm/sec. The force required for it was measured, and the obtained value was made into the probe tack value of the test sample.

<Measurement of adhesive strength of the pressure-sensitive adhesive layer before heat treatment for separation>

On the adhesion surface of the pressure-sensitive adhesive layer formed on the release film, a PET film with a thickness of 50 µm (manufactured by Toyobo Corporation, product name "Cosmoshine A4100") was laminated to obtain a pressure-sensitive adhesive sheet with a substrate.

Then, the release film was removed, and the adhesive surface of the exposed pressure-sensitive adhesive layer was affixed to a stainless steel plate (SUS304 No. 360 polishing) as an adherend, and allowed to stand still for 24 hours in an environment of 23°C and 50% RH (relative humidity). Then, under the same environment, the adhesive force in 23 degreeC was measured by the 180 degree peeling method based on JIS Z0237:2000 at a tensile speed of 300 mm/min.

Details of the adhesive resin, additives, thermally expandable particles, and release material used in the formation of each layer in the following examples are as follows.

<adhesive resin>

Acrylic copolymer (i): 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio) having a structural unit derived from a raw material monomer, Mw60 only acrylic Copolymer.

Acrylic copolymer (ii): consisting of n-butyl acrylate (BA)/methyl methacrylate (MMA)/2-hydroxyethyl acrylate (HEA)/acrylic acid = 86.0/8.0/5.0/1.0 (mass ratio) An acrylic copolymer of only Mw60, which has a structural unit derived from a raw material monomer.

<Additive>

-Isocyanate crosslinking agent (i): Tosoh Corporation make, product name "Colonate L", solid content concentration: 75 mass%.

Photoinitiator (i): BASF company make, product name "Irgacure 184", 1-hydroxy-cyclohexyl-phenyl-ketone.

<Thermal expandable particles>

-Thermally expandable particles (i): Nippon Phillite Co., Ltd., product name "Expancel 031DU40", expansion start temperature (t) = 90°C, average particle diameter (D ₅₀ ) = 22 µm, 90% particle size (D ₉₀ ) = 30 µm.

<Park Lee Jae>

· Middle peeling film: Lintec Co., Ltd. product name "SP-PET382150", a release agent layer formed by a silicone-based release agent on one side of a polyethylene terephthalate (PET) film, thickness: 38 µm.

· Light release film: Lintec Co., Ltd. product name "SP-PET381031", a release agent layer formed on one side of a PET film with a silicone release agent, thickness: 38 µm.

[Example 1]

In the adhesive laminate (1d) shown in Fig. 2(b), a release material is further laminated on the second adhesive layer (X12) of the adhesive sheet (I) and the adhesive layer (X2) of the adhesive sheet (II). An adhesive laminate having one configuration and having an intermediate layer (Z2) formed between the substrate (Y2) of the adhesive sheet (II) and the adhesive layer (X2) was manufactured in the following procedure.

[1] Preparation of adhesive sheet (I)

(1-1) Formation of the first adhesive layer (X11)

To 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin, 5.0 parts by mass (solid content ratio) of the isocyanate-based crosslinking agent (i) is blended, diluted with toluene, and uniformly stirred, and the solid content concentration (effective Component concentration) A pressure-sensitive adhesive composition of 25% by mass was prepared.

Then, the pressure-sensitive adhesive composition was applied to the surface of the release agent layer of the heavy peeling film to form a coating film, and the coating film was dried at 100° C. for 60 seconds, and the first pressure-sensitive adhesive layer (X11) was a non-thermal expandable pressure-sensitive adhesive layer having a thickness of 5 μm. ) Was formed.

In addition, the storage shear modulus G'(23) of the first pressure-sensitive adhesive layer (X11) at 23°C was 2.5×10 ⁵ Pa.

Moreover, the adhesive force of the 1st adhesive layer (X11) measured based on the said method was 0.3 N/25 mm.

(1-2) Formation of the second pressure-sensitive adhesive layer (X12)

To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 0.8 parts by mass (solid content ratio) of the isocyanate-based crosslinking agent (i) is blended, diluted with toluene, and uniformly stirred, and the solid content concentration (effective Component concentration) A pressure-sensitive adhesive composition of 25% by mass was prepared.

Then, the pressure-sensitive adhesive composition was applied to the surface of the release agent layer of the light-release film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a second pressure-sensitive adhesive layer (X12) having a thickness of 10 μm.

Moreover, the storage shear elastic modulus G'(23) of the 2nd adhesive layer (X12) in 23 degreeC was 9.0 x 10 ⁴ Pa.

Moreover, the adhesive force of the 2nd adhesive layer (X12) measured based on the said method was 1.0 N/25 mm.

(1-3) Preparation of base material (Y1)

(1-3-1) Preparation of composition (y1-1)

2-hydroxyethyl acrylate was reacted with the terminal isocyanate urethane prepolymer obtained by reacting an ester-type diol and isophorone diisocyanate (IPDI) to obtain a bifunctional acrylic urethane oligomer having a mass average molecular weight (Mw) of 5000 .

In addition, to 40 mass% (solid content ratio) of the acrylic urethane-based oligomer synthesized above, as an energy ray polymerizable monomer, isobornyl acrylate (IBXA) 40 mass% (solid content ratio), and phenylhydroxypropyl acrylate (HPPA ) 20 mass% (solid content ratio) is blended, and with respect to the total amount (100 mass parts) of the acrylic urethane oligomer and the energy ray polymerizable monomer, further 2.0 mass parts (solid content ratio) of the photoinitiator (i), and As an additive, 0.2 parts by mass (solid content ratio) of a phthalocyanine pigment was blended to prepare an energy ray-curable composition.

And the said thermally expandable particle (i) was blended with the said energy ray-curable composition, and the solvent-free composition (y1-1) which does not contain a solvent was prepared.

In addition, the content of the thermally expandable particles (i) with respect to the total amount (100 mass%) of the composition (y1-1) was 20 mass%.

(1-3-2) Preparation of base material (Y1)

On the surface of a 50 µm-thick polyethylene terephthalate (PET) film (manufactured by Toyobo Corporation, product name "Cosmoshine A4300", probe tack value: 0 mN/5 mmφ), which is a non-thermal expandable substrate, the prepared composition (y1-1 ) Was applied to form a coating film.

Then, using an ultraviolet irradiation device (manufactured by Eye Graphics, product name "ECS-401GX") and a high-pressure mercury lamp (manufactured by Eye Graphics, product name "H04-L41"), illuminance 160 mW/cm 2, light quantity 500 mJ/cm 2 UV irradiation was performed under the conditions of, and the coating film was cured to form a thermally expandable substrate (Y-1) having a thickness of 50 µm. In addition, the said illuminance and light quantity at the time of ultraviolet irradiation are values measured using an illuminance/photometer (manufactured by EIT, product name "UV Power Puck II").

Moreover, the PET film which is the said non-thermal expandable base material corresponds to the non-thermal expandable base material layer (Y1-2).

In addition, as a sample for measuring the physical property value of the thermally expandable substrate layer (Y1-1), the resin composition was applied to the surface of the release agent layer of the light-release film to form a coating film, and the coating film was dried at 100°C for 120 seconds. Then, a 50 µm-thick thermally expandable base layer (Y1-1) was formed in the same manner.

And the storage modulus and probe tack value at each temperature of the thermally expandable base material layer (Y1-1) were measured based on the measurement method mentioned above. The measurement result was as follows.

Storage modulus E'(23) at 23°C = 5.0 × 10 ⁸ Pa

Storage modulus E'(100) at 100°C = 4.0 × 10 ⁶ Pa

Storage modulus E'(208) at 208°C = 4.0 × 10 ⁵ Pa

·Probe tack value = 2 mN/5 ㎜φ

(1-4) Lamination of each layer

While bonding the non-thermal expandable base layer (Y1-2) of the base material (Y1) prepared in (1-3) and the second pressure-sensitive adhesive layer (X12) formed in (1-2), the thermally expandable base material The layer (Y1-1) and the second pressure-sensitive adhesive layer (X12) formed in the above (1-2) were bonded together.

And the light peeling film/second adhesive layer (X12)/non-thermal expandable base layer (Y1-2)/thermal expandable base layer (Y1-1)/first adhesive layer (X11)/heavy release film were laminated in this order. The thus obtained adhesive sheet (I) was produced.

[2] Preparation of adhesive sheet (II)

(2-1) Formation of pressure-sensitive adhesive layer (X2)

To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 8 parts by mass (solid content ratio) of the isocyanate-based crosslinking agent (i) is blended, diluted with toluene, and stirred uniformly, and the solid content concentration (effective Component concentration) A pressure-sensitive adhesive composition of 25% by mass was prepared.

Then, the pressure-sensitive adhesive composition was applied to the surface of the release agent layer of the heavy peeling film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a pressure-sensitive adhesive layer (X2) having a thickness of 20 μm.

Moreover, the adhesive force of the adhesive layer (X2) measured based on the said method was 0.5 N/25 mm.

(2-2) Description (Y2)

The substrate (Y2) was a polyethylene terephthalate (PET) film with a thickness of 50 µm (manufactured by Toyobo Corporation, product name "Cosmoshine A4300", probe tack value: 0 mN/5 mmφ).

(2-3) Intermediate layer (Z2)

(1) Preparation of the composition for forming an intermediate layer

100 parts by mass of the non-energy ray-curable acrylic copolymer C1, 68 parts by mass of the energy ray-curable acrylic copolymer D1, 2.8 parts by mass of a tolylene diisocyanate crosslinking agent (trade name: BHS 8515, manufactured by Toyochem), and the above photopolymerization 2.7 parts by mass of the initiator (i) was added and diluted with ethyl acetate to prepare a solution of the composition for intermediate layer formation having a solid content concentration (active ingredient concentration) of 35% by mass.

(2) Preparation of non-energy ray-curable acrylic copolymer C1

90 parts by mass of butyl acrylate (BA) and 10 parts by mass of acrylic acid (AAc) were added in an ethyl acetate solvent, and 1.0 parts by mass of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and solution polymerization was proceeded. Then, a specific energy ray-curable acrylic copolymer C1 (Mw: 500,000) was obtained.

(3) Preparation of energy ray-curable acrylic copolymer D1

62 parts by mass of butyl acrylate (BA), 10 parts by mass of methyl methacrylate (MMA), and 28 parts by mass of 2-hydroxyethyl acrylate (HEA) were added in an ethyl acetate solvent, and as a polymerization initiator, azobisiso 1.0 mass part of butyronitrile (AIBN) was added, solution polymerization was advanced, and the acrylic copolymer (BA/MMA/HEA = 62/10/28 (mass %)) was obtained after a certain period of time.

Subsequently, to the acrylic copolymer, methacryloyloxyethyl isocyanate in an amount such that 80 equivalents of isocyanate groups per 100 equivalents of the total number of hydroxyl groups in the added HEA was added and reacted, and an energy ray polymerizable group in the side chain The energy ray-curable acrylic copolymer D1 (Mw: 100,000) was obtained. In the energy ray-curable acrylic copolymer D1, the value of β calculated from the formula (2) is 22.4.

(4) Preparation of intermediate layer (Z2)

A solution of the composition for forming an intermediate layer prepared as described above was prepared on the side of the release sheet (manufactured by Lintec, brand name "SP-PET381031", a polyethylene terephthalate film subjected to a silicone release treatment, thickness: 38 µm), The coating film was formed by coating so that the thickness after drying was 45 µm. Next, the coating film was dried at 100° C. for 2 minutes to form an intermediate layer (Z2) to prepare an intermediate layer-forming release sheet.

In addition, about the said intermediate|middle layer formation release sheet, two identical pieces were manufactured, and the intermediate layers of the two intermediate|middle layer formation release sheets were bonded together, and the intermediate layer (Z2) of 90 micrometers in thickness obtained a laminated sheet sandwiched by two release sheets. .

(2-4) Lamination of each layer

The 90-micrometer-thick intermediate layer (Z2) removed one release sheet of the laminated sheet sandwiched by two release sheets, and the substrate (Y2) was laminated on the surface of the exposed intermediate layer (Z2).

Further, the other release sheet was also removed, and on the surface of the exposed intermediate layer (Z2), the adhesive layer (X2) formed in the above (2-1) was bonded to each other, and the substrate (Y2)/intermediate layer (Z2)/adhesive agent The adhesive sheet (II) obtained by laminating the layer (X2)/intermediate release film in this order was prepared.

[3] Preparation of adhesive laminate

The heavy peeling film of the adhesive sheet (I) prepared in the above [1] was removed, the exposed first adhesive layer (X11) and the substrate (Y2) of the adhesive sheet (II) were bonded to each other to obtain an adhesive laminate. .

Peeling force when separating from the interface P of the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) before and after heat treatment with respect to the adhesive laminate (F ₀ ) and (F ₁ ) were measured based on the following method.

As a result, peel force (F ₀ ) = 0.5 N/25 mm, peel force (F ₁ ) = 0 mN/25 mm, and the ratio of peel force (F ₁ ) and peel force (F ₀ ) [(F ₁ )/(F ₀ )] was 0.

<Measurement of peeling force (F ₀ )>

The produced adhesive laminate was stopped still for 24 hours in an environment of 23°C and 50% RH (relative humidity), and then the heavy peeling film of the adhesive sheet (II) of the adhesive laminate was removed, and the exposed adhesive layer ( X2) was affixed to a stainless steel plate (SUS304, No. 360 polishing).

Next, the end of the stainless steel plate to which the adhesive laminate was affixed was fixed to the lower chuck of a universal tensile tester (manufactured by Orientec, product name "Tensilon UTM-4-100").

In addition, the adhesive sheet of the adhesive laminate in the upper chuck of the universal tensile tester so as to be peeled off at the interface P of the first adhesive layer (X11) of the adhesive sheet (I) of the adhesive laminate and the substrate (Y2) of the adhesive sheet (II) (I) was fixed.

And under the same environment as above, based on JIS Z0237:2000, the peeling force measured at the time of peeling at the interface P at a tensile speed of 300 mm/min by a 180° peeling method was referred to as “peel force (F ₀ )”. I did it.

<Measurement of peeling force (F ₁ )>

The heavy peeling film of the PSA sheet (II) of the produced PSA laminate was removed, and the exposed PSA layer (X2) was affixed to a stainless steel plate (SUS304, No. 360 polishing).

Then, the stainless steel sheet and the adhesive laminate were heated at 240° C. for 3 minutes to expand the thermally expandable particles in the thermally expandable base layer (Y1-2) of the adhesive laminate.

After that, in the same manner as in the measurement of the peeling force (F ₀ ) described above, under the conditions described above, the interface between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) The peeling force measured when peeling from P was made into "peeling force (F ₁ )".

In addition, in the measurement of the peel force (F ₁ ), when trying to fix the adhesive sheet (I) of the adhesive laminate in the upper chuck of the universal tensile tester, the adhesive sheet (I) is completely separated at the interface P. When it was impossible to fix, the measurement was terminated, and the peeling force (F ₁ ) at that time was set to "0 mN/25 mm".

[Example 2]

By the following procedure, the adhesive sheet (II) in the state in which the object to be processed was affixed was produced.

(1) Fixing of semiconductor wafers

The light peeling film of the adhesive laminate prepared in Example 1 was removed, and the adhesive surface of the 2nd adhesive layer (X12) of the adhesive sheet (I) exposed was affixed with a support body (glass).

Then, the surface on the circuit surface side of the semiconductor wafer having the patterned circuit surface and the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) were bonded, and the semiconductor wafer was fixed to the support through the pressure-sensitive adhesive laminate prepared in Example 1. Made it.

(2) formation of modified regions

Using a stealth laser irradiation device (manufactured by Tokyo Precision Co., Ltd., device name "ML300PlusWH"), stealth laser irradiation is performed from the side opposite to the circuit formation surface of the semiconductor wafer to form a modified region that serves as the starting point for division inside the semiconductor wafer. I did.

(3) Separation at the interface P

After the above (2), the adhesive laminate was subjected to a heat treatment for 3 minutes at 120° C. at which the expansion start temperature of the thermally expandable particles (90° C.) or higher. And, at the interface P of the 1st adhesive layer (X11) of the adhesive sheet (I), and the base material (Y2) of the adhesive sheet (II), it could be easily separated collectively.

Then, after separation, a pressure-sensitive adhesive sheet (II) in a state in which a semiconductor wafer having a modified region formed therein was affixed was obtained.

1a, 1b, 1c, 1d, 2 adhesive laminate
(I) adhesive sheet
(X1) adhesive layer
(X11) 1st adhesive layer
(X12) 2nd adhesive layer
(Y1) description
(Y1-1) Thermally expandable substrate layer
(Y1-2) Non-thermal expandable base layer
(II) adhesive sheet
(X2) adhesive layer
(Z2) middle layer
(Y2) description
50 support
60, 70 object to be processed
61 Hardened Encapsulant
Reorganized cargo of 61a hardened encapsulant
71 modified area
72 gap

Claims (17)

Having a substrate (Y1) and a pressure-sensitive adhesive layer (X1), a thermally expandable pressure-sensitive adhesive sheet (I) containing thermally expandable particles having a thermal expansion initiation temperature (t) in any layer, and a substrate (Y2) and pressure-sensitive adhesive layer (X2) Using an adhesive laminate comprising an adhesive sheet (II) and directly laminating the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) to produce a processed product subjected to at least any processing of cutting and grinding As a way to do it,
Having the following steps (1) to (3) in this order,
Process (1): a step of affixing the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and affixing the object to be processed on the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate
Process (2): A process of performing one or more processing on the object to be processed
Step (3): The adhesiveness while maintaining a state in which the object to be processed is affixed to the surface of the adhesive layer (X2) of the adhesive laminate by heating at or above the thermal expansion initiation temperature (t) of the thermally expandable particles. Step of separating the laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II)
In addition, it has the following process (4),
Process (4): A process of performing at least one of cutting and grinding on the surface of the object on the opposite side to the adhesive layer (X2) of the object to be applied.
The said process (4) is performed in at least any one of following (X) and (Y), The manufacturing method of a processed product.
(X): As the one or more processing, it is carried out in the step (2).
(Y): It is implemented after the said process (3) The method of claim 1,
The manufacturing method, wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270°C. The method according to claim 1 or 2,
The manufacturing method in which the base material (Y1) of the adhesive sheet (I) has a thermally expandable base material layer (Y1-1) containing the thermally expandable particles. The method of claim 3,
The manufacturing method in which the base material (Y1) which the adhesive sheet (I) has has a thermally expandable base material layer (Y1-1) and a non-thermal expandable base material layer (Y1-2). The method according to claim 3 or 4,
A manufacturing method in which the thermally expandable base layer (Y1-1) of the base material (Y1) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) are directly laminated. The method according to any one of claims 3 to 5,
The adhesive sheet (I) has a configuration in which the substrate (Y1) is sandwiched by the first adhesive layer (X11) and the second adhesive layer (X12),
The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) have a structure in which they are directly laminated,
The production method, wherein the surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface affixed to the support. The method according to claim 1 or 2,
The first adhesive layer (X11) is a thermally expandable adhesive layer containing the thermally expandable particles,
The second adhesive layer (X12) is a non-thermal expandable adhesive layer,
The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) have a structure in which they are directly laminated,
The manufacturing method, wherein the surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface affixed to the support. The method according to claim 6 or 7,
The manufacturing method, wherein the surface on the side on which the first pressure-sensitive adhesive layer (X11) of the substrate (Y1) is laminated is a surface subjected to an easy adhesion treatment. The method according to any one of claims 1 to 8,
The manufacturing method in which the surface on the side where the adhesive sheet (I) of the base material (Y2) is laminated is a surface subjected to a peeling treatment. The method according to any one of claims 1 to 9,
The manufacturing method in which the pressure-sensitive adhesive sheet (II) has an intermediate layer (Z2) between the substrate (Y2) and the pressure-sensitive adhesive layer (X2). The method according to any one of claims 1 to 10,
The manufacturing method in which the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is an energy ray-curable pressure-sensitive adhesive layer. The method according to any one of claims 1 to 11,
The production method in which the pressure-sensitive adhesive sheet (II) satisfies one or more of the following requirements (α) to (γ).
-Requirement (α): The Young's modulus of the substrate (Y2) is 1.0 MPa or more.
-Requirement (β): The thickness of the substrate (Y2) is 5 µm or more.
Requirement (γ): The storage modulus G'(23°C) of the pressure-sensitive adhesive layer (X2) is 0.1 MPa or more. The method according to any one of claims 1 to 12,
The object to be processed is a semiconductor wafer,
The one or more processing in the step (2) includes the following step (2-A),
Process (2-A): A process of forming a modified region serving as a division starting point on the semiconductor wafer
The said process (4) is the following process (4-A),
Process (4-A): A process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2)
The production method, wherein the step (4-A) is carried out in the following (XA) or (YA).
(XA): The one or more processing is performed after the step (2-A)
(YA): It is carried out after the above step (3) The method according to any one of claims 1 to 12,
The object to be processed is a semiconductor chip,
The one or more processing in the step (2) includes the following step (2-B),
Process (2-B): of the adhesive surfaces of the semiconductor chip and the pressure-sensitive adhesive layer (X2), the periphery of the semiconductor chip is covered with a sealing material, the sealing material is cured, and the semiconductor chip is applied to the cured sealing material. Process of obtaining a cured sealing body formed by sealing
The said process (4) is performed in at least any one of following (XB) and (YB), The manufacturing method.
(XB): The one or more processing is carried out after the step (2-B)
(YB): It is implemented after the said process (3) The method according to any one of claims 1 to 12,
A semiconductor wafer having a modified region in which the object to be processed is a division starting point,
The manufacturing method, wherein the step (4) is the following step (4-A).
Process (4-A): The process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2) The method according to any one of claims 1 to 12,
The object to be processed is a semiconductor wafer having a cutout groove serving as a division starting point,
The manufacturing method, wherein the step (1) is the following step (1-C), and the step (4) is the following step (4-C).
Step (1-C): A surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate is affixed to the support, and the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive laminate has a cutout groove of the semiconductor wafer Process of attaching
Process (4-C): A process of grinding the surface of the semiconductor wafer on the opposite side to the adhesive layer (X2) It has a base material (Y1) and a pressure-sensitive adhesive layer (X1), and a thermally expandable pressure-sensitive adhesive sheet (I) containing thermally expandable particles in any layer, and a pressure-sensitive adhesive sheet (II) having a base material (Y2) and pressure-sensitive adhesive layer (X2) And, the adhesive laminated body for producing a processed article which has been subjected to at least any of cutting and grinding, wherein the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) are directly laminated.

Images